[0001] The present invention relates to monocyclopentadienyl complexes in which the cyclopentadienyl
system bears at least one bridged donor and at least one arylalkyl group and to a
catalyst system comprising at least one of the monocyclopentadienyl complexes, and
also to methods of preparing them.
[0002] In addition, the invention provides for the use of the catalyst system for the polymerization
or copolymerization of olefins and provides a process for preparing polyolefins by
polymerization or copolymerization of olefins in the presence of the catalyst system
and provides polymers obtainable in this way.
[0003] Many of the catalysts used for the polymerization of α-olefins are based on immobilized
chromium oxides (cf., for example,
Kirk-Othmer, "Encyclopedia of Chemical Technology", 1981, Vol.16, p. 402). These generally give ethylene homopolymers and copolymers having high molecular
weights but are relatively insensitive to hydrogen and thus do not allow the molecular
weight to be controlled in a simple fashion. In contrast, the molecular weight of
polyethylene can be controlled in a simple way by addition of hydrogen when using
bis(cyclopentadienyl)chromium (
US 3,709,853), bis(indenyl)chromium or bis(fluorenyl)chromium (
US 4,015,059) applied to an inorganic, oxidic support.
[0004] As in the case of the Ziegler-Natta systems, there is now also a search for catalyst
systems having a uniquely defined, active center, known as single site catalysts,
in the case of the chromium compounds. The intention is to allow the activity, copolymerization
behavior of the catalyst and the properties of the polymers obtained in this way to
be altered in a simple fashion by targeted variation of the ligand framework.
[0005] DE 197 10615 describes monocyclopentadienylchromium compounds substituted by donor ligands which
can be used for the polymerization of both ethene and propene. The donor is in this
case from group 15 and uncharged. The donor is bound to the cyclopentadienyl ring
via a (ZR
2)
n fragment, where R is hydrogen, alkyl or aryl, Z is an atom of group 14 and n is 1.
DE 196 30 580 specifically claims complexes in which Z is carbon and the donor is an amine.
[0006] WO 96/13529 describes reduced transition metal complexes of elements of groups 4 to 6 of the
Periodic Table with polydentate monoanionic ligands. These also include cyclopentadienyl
ligands containing a donor function. The examples are restricted to titanium compounds.
[0007] WO01/12641 describes monocyclopentadienyl complexes of chromium, molybdenum and tungsten which
bear, in particular, quinolyl or pyridyl donors which are bound either directly or
via a C
1 or Si bridge to the cyclopentadienyl system.
[0008] WO 01/92346 discloses cyclopentadienyl complexes of elements of groups 4-6 of the Periodic Table
of the Elements in which a dihydrocarbyl-Y group, where Y is an element of group 14
of the Periodic Table of the Elements, which bears particular Lewis bases is bound
to the cyclopentadienyl system.
[0009] The abovementioned catalyst systems are not yet optimized in terms of their activities.
Furthermore, the polymers and copolymers formed usually have very high molecular weights.
[0010] It is an object of the present invention to discover further transition metal complexes
based on cyclopentadienyl ligands bearing a bridged donor which are suitable for the
polymerization of olefins and display very high activities. A further object of the
invention is to find an advantageous process for preparing such complexes.
[0011] We have found that this object is achieved by monocyclopentadienyl complexes according
to
claim 1.
[0012] Furthermore, we have found a catalyst system comprising the monocyclopentadienyl
complexes of the present invention, the use of the monocyclopentadienyl complexes
or of the catalyst system for the polymerization or copolymerization of olefins and
a process for preparing polyolefins by polymerization or copolymerization of olefins
in the presence of the monocyclopentadienyl complex or of the catalyst system and
polymers obtainable in this way. Furthermore, a process and intermediates in this
process have been found.
[0013] The monocyclopentadienyl complexes can be in monomeric, dimeric or oligomeric form.
The monocyclopentadienyl complexes are preferably in monomeric form.
[0014] m can be 1, 2 or 3, i.e. 1, 2 or 3 donor groups Y can be bound to Cp . If 2 or 3
Y groups are present, these can be identical or different. Preference is given to
only one donor group Y being bound to Cp (m = 1).
[0015] In preferred cyclopentadienyl systems Cp, all E
1A to E
5A are carbon.
[0016] One of the substituents R
1A-R
4A is always an alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and
6-20 carbon atoms in the aryl radical in order to achieve the desired results. The
remaining substituents can be varied widely and possible carboorganic substituents
R
1A-R
4A are, for example, the following; C
1-C
22-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl,
5- to 7-membered cycloalkyl which may in turn bear a C
1-C
10-alkyl group and/or a C
6-C
10-aryl group as substituent, e.g. cyclopropane, cyclobutane cyclopentane, cyclohexane,
cycloheptane, cyclooctane, cyclononane or cyclododecane, C
2-C
22-alkenyl which may be linear, cyclic or branched and in which the double bond can
be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl,
hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C
6-C
22-aryl which may be substituted by further alkyl groups, e.g. phenyl, naphthyl, biphenyl,
anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or 2,6-dimethylphenyl, 2,3,4-,
2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, or arylalkyl which may be
substituted by further alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1- or 2-ethylphenyl,
where two of the radicals R
1A to R
4A may also be joined to form a 5-, 6- or 7-membered ring and/or two of the vicinal
radicals R
1A-R
4A may be joined to form a five-, six- or seven-membered heterocycle which contains
at least one atom from the group consisting of N, P, O or S and/or the organic radicals
R
1A-R
4A may also be substituted by halogens such as fluorine, chlorine or bromine. Furthermore,
R
1A-R
4A can also be amino NR
5A2, or N(SiR
5A3)
2, alkoxy or aryloxy OR
5A, for example dimethylamino, N-pyrrolidinyl, picolinyl, methoxy, ethoxy or isopropoxy.
In organosilicon substituents SiR
5A3, the radicals R
5A can be the same carboorganic radicals as described in more detail above for R
1A-R
4A, where two R
5A may also be joined to form a 5- or 6-membered ring, e.g. trimethylsilyl, triethylsilyl,
butyldimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl, triphenylsilyl
or dimethylphenylsilyl. These SiR
5A3 radicals can also be bound to the cyclopentadienyl skeleton via an oxygen or nitrogen,
for example trimethylsilyloxy, triethylsilyloxy, butyldimethylsilyloxy, tributylsilyloxy
or tri-tert-butylsilyloxy. Preferred radicals R
1A-R
4A are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl,
n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, ortho-dialkyl-
or -dichloro-substituted phenyls, trialkyl- or trichloro-substituted phenyls, naphthyl,
biphenyl and anthranyl. Particularly useful organosilicon substituents are trialkylsilyl
groups having from 1 to 10 carbon atoms in the alkyl radical, in particular trimethylsilyl
groups.
[0017] Two vicinal radicals R
1A-R
4A together with the atoms E
1A-E
5A bearing them can form a heterocycle, preferably a heteroaromatic, which contains
at least one atom from the group consisting of nitrogen, phosphorus, oxygen and sulfur,
particularly preferably nitrogen and/or sulfur, with preference being given to the
atoms E
1A-E
5A present in the heterocycle or heteroaromatic being carbon. Preference is given to
heterocycles and heteroaromatics having a ring size of 5 or 6 ring atoms. Examples
of 5-membered heterocycles which have from one to four nitrogen atoms and/or a sulfur
or oxygen atom in addition to carbon atoms as ring members are 1,2-dihydrofuran, furan,
thiophene, pyrrole, isoxazole, 3-isothiazole, pyrazole, oxazole, thiazole, imidazole,
1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-triazole and 1,2,4-triazole.
Examples of 6-membered heteroaryl groups which may contain from one to four nitrogen
atoms and/or a phosphorus atom are pyridine, phosphobenzene, pyridazine, pyrimidine,
pyrazine, 1,3,5-triazine, 1,2,4-triazine or 1,2,3-triazine. The 5-membered and 6-membered
heterocycles can also be substituted by C
1-C
10-alkyl, C
6-C
10-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and 6-10 carbon
atoms in the aryl radical, trialkylsilyl or halogens such as fluorine, chlorine or
bromine, dialkylamide, alkylarylamide, diarylamide, alkoxy or aryloxy or be fused
with one or more aromatics or heteroaromatics. Examples of benzo-fused 5-membered
heteroaryl groups are indole, indazole, benzofuran, benzothiophene, benzothiazole,
benzoxazole and benzimidazole. Examples of benzo-fused 6-membered heteroaryl groups
are chromane, benzopyran, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline,
quinoxaline, 1,10-phenanthroline and quinolizine. Naming and numbering of the heterocycles
has been taken from Lettau,
Chemie der Heterocyclen, 1st edition, VEB, Weinheim 1979. The heterocycles/heteroaromatics are preferably fused with the cyclopentadienyl
skeleton via a C-C double bond of the heterocycle/heteroaromatic. Heterocycles/heteroaromatics
having one heteroatom are preferably 2,3- or b-fused.
[0018] Cyclopentadienyl systems Cp having a fused heterocycle are, for example, thiapentalene,
methylthiapentalene, ethylthiapentalene, isopropylthiapentalene, n-butylthiapentalene,
tert-butylthiapentalene, trimethylsilylthiapentalene, phenylthiapentalene, naphthylthiapentalene,
methylthiopentalene, azapentalene, methylazapentalene, ethylazapentalene, isopropylazapentalene,
n-butylazapentalene, trimethylsilylazapentalene, phenylazapentalene, naphthylazapentalene,
oxapentalene or phosphapentalene.
[0020] Particularly preferred substituents R
1A-R
4A are the above-described carboorganic substituents and the carboorganic substituents
which form a cyclic fused ring system, i.e. together with the E
1A-E
5A skeleton, preferably together with a C
5cyclopentadienyl skeleton, form, for example, an unsubstituted or substituted indenyl,
benzindenyl, phenanthrenyl or tetrahydroindenyl system, and in particular their preferred
embodiments.
[0021] Examples of such cyclopentadienyl systems (without the group -Z-A-, which is preferably
located in the 1 position, and without the arylalkyl substituents) are monoalkylcyclopentadienyl
systems, e.g. 3-methylcyclopentadienyl, 3-ethylcyclopentadienyl, 3-isopropylcyclopentadienyl,
3-tert-butylcyclopentadienyl, dialkylcyclopentadienyl systems, e.g. tetrahydroindenyl,
2,4-dimethylcyclopentadienyl or 3-methyl-5-tert-butylcyclopentadienyl, or trialkylcyclopentadienyl
systems, e.g. 2,3,5-trimethylcyclopentadienyl, and also indenyl or benzoindenyl. The
fused ring system may bear further C
1-C
20-alkyl, C
2-C
20-alkenyl, C
6-C
20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon
atoms in the aryl radical, NR
5A2, N(SiR
5A3)
2, OR
5A, OSiR
5A3 or SiR
5A3 substituents, e.g. 4-methylindenyl, 4-ethylindenyl, 4-isopropylindenyl, 5-methylindenyl,
4-phenylindenyl, 5-methyl-4-phenylindenyl or 4-naphthylindenyl.
[0022] One of the substituents R
1A-R
4A, preferably R
2A, is an arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon
atoms in the aryl radical, preferably C
6-C
14-aryl, for example benzyl, phenylethyl, naphthylmethyl, anthracenylmethyl or phenanthrenylmethyl,
where the aryl may also be substituted by N-, P-, O- or S-containing substituents,
C
1-C
22-alkyl, C
2-C
22-alkenyl, halogens or haloalkyls or haloaryls having 1-10 carbon atoms, for example
o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5- or 2,6-dimethylbenzyl, 2,3,4-, 2,3,5-, 2,3,6-,
2,4,5-, 2,4,6- or 3,4,5-trimethylbenzyl, o-, m-, p-dimethylaminobenzyl, o-, m-, p-methoxybenzyl,
o-, m-, p-fluorobenzyl, o-, m-, p-chlorobenzyl, o-, m-, p-trifluoromethylbenzyl, 2,3-,
2,4-, 2,5- or 2,6-difluorobenzyl, 2,3-, 2,4-, 2,5- or 2,6-dichlorobenzyl or 2,3-,
2,4-, 2,5-, or 2,6-di(trifluoromethyl)benzyl. The N-, P-, O- or S-containing substituents,
preferably NR
5A2, N(SiR
5A3)
2, OR
5A or OSiR
5A3, C
1-C
22-alkyl, C
2-C
22-alkenyl, halogens or haloalkyls or haloaryls having 1-10 carbon atoms as substituents
on the aryl radical are preferably located in the ortho and/or para position relative
to the bond to the alkyl radical which is bound to the cyclopentadienyl ring. -Z-A
and the arylalkyl substituent being are located in the 1,3 positions relative to one
another on the cyclopentadienyl ring.
[0023] As in the cases of the metallocenes, the monocyclopentadienyl complexes of the present
invention can be chiral. Thus, either one of the substituents R
1A-R
4A on the cyclopentadienyl skeleton can bear one or more chiral centers or else the
cyclopentadienyl system Cp can itself be enantiotopic, so that the chirality is induced
only when it is bound to the transition metal M (for the conventions regarding chirality
in cyclopentadienyl compounds, see
R. Halterman, Chem. Rev. 92, (1992), 965-994).
[0024] The bridge Z between the cyclopentadienyl system Cp and the uncharged donor A is
an organic divalent bridge (k=1), preferably consisting of carbon- and/or silicon-
and/or boron-containing bridge members. Changing the length of the link between the
cyclopentadienyl system and A enables the activity of the catalyst to be influenced.
[0025] Possible carboorganic substituents R
6A-R
11A on the link Z are, for example the following: hydrogen, C
1-C
20-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl,
5- to 7-membered cycloalkyl which may in turn bear a C
6-C
10-aryl group as substituent, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C
2-C
20-alkenyl which may be linear, cyclic or branched and in which the double bond can
be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl,
hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C
6-C
20-aryl which may be substituted by further alkyl groups, e.g. phenyl, naphthyl, biphenyl,
anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or 2,6-dimethylphen-1-yl, 2,3,4-,
2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphen-1-yl, or arylalkyl which may
be substituted by further alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1- or
2-ethylphenyl, where two radicals R
6A to R
11A may also be joined to form a 5- or 6-membered ring, for example cyclohexane, and
the organic radicals R
6A-R
11A may also be substituted by halogens such as fluorine, chlorine or bromine, for example
pentafluorophenyl or bis-3,5-trifluoromethylphen-1-yl, and alkyl or aryl.
[0026] In organosilicon substituents SiR
12A3, possible radicals R
12A are the same radicals mentioned in more detail above for R
6A-R
11A, where two R
12A may also be joined to form a 5- or 6-membered ring, e.g. trimethylsilyl, triethylsilyl,
butyldimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl, triphenylsilyl
or dimethylphenylsilyl. Preferred radicals R
12A are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl,
n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, ortho-dialkyl- or-dichloro-substituted
phenyls, trialkyl- or trichloro-substituted phenyls, naphthyl, biphenyl and anthranyl.
[0027] Particularly preferred substituents R
6A to R
11A are hydrogen, C
1-C
20-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl
C
6-C
20-aryl which may be substituted by further alkyl groups, e.g. phenyl, naphthyl, biphenyl,
anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-, or 2,6-dimethylphen-1-yl, 2,3,4-,
2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphen-1-yl, or arylalkyl which may
be substituted by further alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1- or
2-ethylphenyl, where two radicals R
6A to R11A may also be joined to form a 5- or 6-membered ring, for example cyclohexane,
and the organic radicals R
6A-R
11A may also be substituted by halogens such as fluorine, chlorine or bromine, in particular
fluorine, for example pentafluorophenyl or bis-3,5-trifluoromethylphen-1-yl, and alkyl
or aryl. Particular preference is given to methyl, ethyl, 1-propyl, 2-isopropyl, 1-butyl,
2-tert-butyl, phenyl and pentafluorophenyl.
[0028] Z is preferably a -CR
6AR
7A- or -SiR
6AR
7A- group, in particular -Si(CH
3)
2-, -CR
6AR7
ACR
8AR
9A-, -SiR
6AR
7ACR
8AR
9A- or substituted or unsubstituted 1,2-phenylene and in particular -CR
6AR
7A-. Here, the preferred embodiments of the substituents R
6A to R
11A described above are likewise preferred embodiments. -CR
6AR
7A- is preferably a -CHR
6A-, -CH
2- or -C(CH
3)
2- group. The group -SiR
6AR
7A- in -L
1AR
6AR
7ACR
8AR
9A- can be bound to the cyclopentadienyl system or to A. This group -SiR
6AR
7A- or its preferred embodiments is preferably bound to Cp.
[0029] k is 0 or 1, and is in particular equal to 1 or when A is an unsubstituted, substituted
or fused, heterocyclic ring system can also be 0.
[0030] A is a group of the formula (IVa) or (IVb)
where
- E6A-E11A
- are each, independently of one another, carbon or nitrogen,
- R16A-R21
- are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon
atoms in the aryl radical or SiR22A3, where the organic radicals R16A-R21A may also be substituted by halogens or nitrogen and further C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon
atoms in the aryl radical or SiR22A3 groups and two vicinal radicals R16A-R21A or R16A and Z may also be joined to form a five- or six-membered ring and
- the radicals R22A
- are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and 6-20
carbon atoms in the aryl radical and two radicals R22A may also be joined to form a five- or six-membered ring and
- p
- is 0 when E6A-E11A is nitrogen and is 1 when E6A-E11A is carbon.
[0031] In particular, 0 or 1 of E
6A-E
11A is nitrogen and the remainder are carbon. A is particularly preferably 2-pyridyl,
6-methyl-2-pyridyl, 4-methyl-2-pyridyl, 5-methyl-2-pyridyl, 5-ethyl-2-pyridyl, 4,6-dimethyl-2-pyridyl,
3-pyridazyl, 4-pyrimidyl, 6-methyl-4-pyrimidyl, 2-pyrazinyl, 6-methyl-2-pyrazinyl,
5-methyl-2-pyrazinyl, 3-methyl-2-pyrazinyl, 3-ethylpyrazinyl, 3,5,6-trimethyl-2-pyrazinyl,
2-quinolyl, 4-methyl-2-quinolyl, 6-methyl-2-quinolyl, 7-methyl-2-quinolyl, 2-quinoxalyl
or 3-methyl-2-quinoxalyl.
[0032] Owing to the ease of preparation, a preferred combination of Z and A is when Z is
an unsubstituted or substituted 1,2-phenylene group and A is NR
16AR
17A, and also the combination in which Z is -CHR
6A-, -CH
2-, -C(CH
3)
2 or -Si(CH
3)
2- and A is unsubstituted or substituted 2-quinolyl or unsubstituted or substituted
2-pyridyl. Systems which do not have a bridge Z and in which k is O are also particularly
simple to obtain. In this case, A is preferably a substituent of the formula (IVb)
and in particular unsubstituted or substituted 8-quinolyl. The above-described preferred
embodiments of the variables are also preferred in these preferred combinations.
[0033] M
A is a metal selected from the group consisting of titanium in the oxidation state
3, vanadium, chromium, molybdenum and tungsten, preferably titanium in the oxidation
state 3 and chromium. Particular preference is given to chromium in the oxidation
states 2, 3 and 4, in particular 3. The metal complexes, in particular the chromium
complexes, can be obtained in a simple manner by reacting the corresponding metal
salts, e.g. metal chlorides, with the ligand anion (e.g. using a method analogous
to the examples in
DE 197 10615).
[0034] The embodiments and preferred embodiments of Cp, Y, Z, A, m and M
A indicated above also apply individually and in combination to these preferred monocyclopentadienyl
complexes.
[0035] The ligands X
A result from, for example, the choice of the metal compounds used as starting materials
for the synthesis of the monocyclopentadienyl complexes, but can also be varied subsequently.
Possible ligands X
A are, in particular, the halogens such as fluorine, chlorine, bromine or iodine, in
particular chlorine. Alkyl radicals such as methyl, ethyl, propyl, butyl, vinyl, allyl,
phenyl or benzyl are also advantageous ligands X
A. As further ligands X
A, mention may be made, purely by way of example and in no way exhaustively, of trifluoroacetate,
BF
4-, PF
6- and weakly coordinating or noncoordinating anions (cf., for example, S. Strauss in
Chem. Rev. 1993, 93, 927-942) such as B(C
6F
5)
4-.
[0036] Amides, alkoxides, sulfonates, carboxylates and β-diketonates are also particularly
suitable ligands X
A. Variation of the radicals R
23A and R
24A makes it possible, for example, to make fine adjustments in physical properties such
as solubility. Possible carboorganic substituents R
23A-R
24A are, for example, the following: C
1-C
20-alkyl which may be linear or branched, e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl,
5- to 7-membered cycloalkyl which may in turn bear a C
6-C
10-aryl group as substituent, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C
2-C
20-alkenyl which may be linear, cyclic or branched and in which the double bond may
be internal or terminal, e.g. vinyl, 1-allyl, 2-allyl, 3-allyl, butenyl, pentenyl,
hexenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl or cyclooctadienyl, C
6-C
20-aryl which may be substituted by further alkyl groups and/or N- or O-containing radicals,
e.g. phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl, 2,3-, 2,4-, 2,5-,
or 2,6-dimethylphenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl,
2-methoxyphenyl, 2-N,N-dimethylaminophenyl, or arylalkyl, which may be substituted
by further alkyl groups, e.g. benzyl, o-, m-, p-methylbenzyl, 1-or 2-ethylphenyl,
where R
23A may also be joined to R
24A to form a 5- or 6-membered ring and the organic radicals R
23A-R
24A may also be substituted by halogens such as fluorine, chlorine or bromine. In organosilicon
substituents SiR
25A3, the radicals R
25A can be the same radicals described in more detail above for R
23A-R
24A, where two radicals R
25A may also be joined to form a 5- or 6-membered ring, e.g. trimethylsilyl, triethylsilyl,
butyldimethylsilyl, tributylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl.
Preference is given to using C
1-C
10-alkyl such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl,
n-octyl, and also vinyl, allyl, benzyl and phenyl as radicals R
23A and R
24A. Some of these substituted ligands X are particularly preferably used because they
are obtainable from cheap and readily available starting materials. Thus, a particularly
preferred embodiment is that in which X
A is dimethylamide, methoxide, ethoxide, isopropoxide, phenoxide, naphthoxide, triflate,
p-toluolenesulfonate, acetate or acetylacetonate.
[0037] The number n of the ligands X
A depends on the oxidation state of the transition metal M
A. The number n can therefore not be given in general terms. The oxidation state of
the transition metals M
A in catalytically active complexes is usually known to those skilled in the art. Chromium,
molybdenum and tungsten are very probably present in the oxidation state +3 and vanadium
in the oxidation state +3 or +4. However, it is also possible to use complexes whose
oxidation state does not correspond to that of the active catalyst. Such complexes
can then be appropriately reduced or oxidized by means of suitable activators. Preference
is given to using chromium complexes in the oxidation state +3 and titanium complexes
in the oxidation state 3.
[0038] Preferred monocyclopentadienyl complexes A) of this type are:
1-(8-quinolyl)-3-benzylcyclopentadienylchromium(III) dichloride, 1-(8-quinolyl)-3-(1-naphthylmethyl)cyclopentadienylchromium(III)
dichloride, 1-(8-quinolyl)-3-(4-trifluoromethylbenzylcyclopentadienylchromium(III)
dichloride, 1-(8-quinolyl)-3-(4-chlorobenzyl)cyclopentadienylchromium(III) dichloride,
1-(8-quinolyl)-2-methyl-3-benzylcyclopentadienylchromium(III) dichloride, 1-(8-quinolyl)-2-methyl-3-(1-naphthylmethyl)cyclopentadienylchromium(III)
dichloride, 1-(8-quinolyl)-2-methyl-3-(4-trifluoromethylphenylmethyl)cyclopentadienylchromium(III)
dichloride, 1-(8-quinolyl)-2-methyl-3-(4-chlorophenyl)methyl)cyclopentadienylchromium(III)
dichloride, 1-(8-quinolyl)-2-benzylindenylchromium(III) dichloride, 1-(8-quinolyl)-2-benzylbenzindenylchromium(III)
dichloride, 1-(8-(2-methylquinolyl))-2-methyl-3-benzylcyclopentadienylchromium(III)
dichioride, 1-(8-(2-methylquinolyl))-2-benzylindenylchromium(III) dichloride, 1-(2-pyridylmethyl)-3-benzylcyclopentadienylchromium(III)
dichloride, 1-(2-pyridylmethyl)-2-methyl-3-benzylcyclopentadienylchromium(III) dichloride,
1-(2-quinolylmethyl)-3-benzylcyclopentadienylchromium dichloride, 1-(2-pyridylethyl)-3-benzylcyclopentadienylchromium
dichloride, 1-(2-pyridyl-1-methylethyl)-3-benzylcyclopentadienylchromium dichloride
or 1-(2-pyridyl-1-phenylmethyl)-3-benzylcyclopentadienylchromium dichloride.
[0039] The synthesis of such complexes can be carried out by methods known per se, with
preference being given to reacting the appropriately substituted cyclopentadienyl
anions with halides of titanium, vanadium or chromium. Examples of appropriate preparative
methods are described, inter alia, in the
Journal of Organometallic Chemistry, 369 (1989), 359-370, and in
EP-A-1212333.
[0040] The monocyclopentadienyl complexes of the present invention can be used alone or
together with further components as catalyst system for olefin polymerization. We
have also found catalyst systems for olefin polymerization comprising
- A) at least one monocyclopentadienyl complex according to the present invention,
- B) optionally an organic or inorganic support,
- C) optionally one or more activating compounds,
- D) optionally one or more catalysts suitable for olefin polymerization and
- E) optionally one or more metal compounds containing a metal of group 1, 2 or 13 of
the Periodic Table.
[0041] Thus, more than one of the monocyclopentadienyl complexes of the present invention
can simultaneously be brought into contact with the olefin or olefins to be polymerized.
This has the advantage that a wide range of polymers can be produced in this way.
For example, bimodal products can be prepared in this way.
[0042] For the monocyclopentadienyl complexes of the present invention to be able to be
used in polymerization processes in the gas phase or in suspension, it is often advantageous
for them to be used in the form of a solid, i.e. for them to be applied to a solid
support B). Furthermore, the supported monocyclopentadienyl complexes have a high
productivity. Consequently, the monocyclopentadienyl complexes of the present invention
can, if desired, also be immobilized on an organic or inorganic support B) and be
used in supported form in the polymerization. This enables, for example, deposits
in the reactor to be avoided and the polymer morphology to be controlled. As support
materials, preference is given to using silica gel, magnesium chloride, aluminum oxide,
mesoporous materials, aluminosilicates, hydrotalcites and organic polymers such as
polyethylene, polypropylene, polystyrene, polytetrafluoroethylene or polymers bearing
polar functional groups, for example copolymers of ethene and acrylic esters, acrolein
or vinyl acetate.
[0043] Particular preference is given to a catalyst system comprising a monocyclopentadienyl
complex according to the present invention and at least one activating compound C)
together with a support component B).
[0044] To obtain such a supported catalyst system, the unsupported catalyst system can be
reacted with a support component B). The order in which support component B), monocyclopentadienyl
complex A) according to the present invention and the activating compound C) are combined
is in principle immaterial. The monocyclopentadienyl complex A) of the present invention
and the activating compound C) can be immobilized independently of one another or
simultaneously. After the individual process steps, the solid can be washed with suitable
inert solvents, e.g. aliphatic or aromatic hydrocarbons.
[0045] In a preferred method of preparing the supported catalyst system, at least one of
the monocyclopentadienyl complexes of the present invention is brought into contact
with at least one activating compound C) in a suitable solvent, preferably giving
a soluble reaction product, an adduct or a mixture. The preparation obtained in this
way is then mixed with the dehydrated or passivated support material, the solvent
is removed and the resulting supported monocyclopentadienyl catalyst system is dried
to ensure that all or most of the solvent is removed from the pores of the support
material. The supported catalyst is obtained as a free-flowing powder. Examples of
the industrial implementation of the above process are described in
WO 96/00243,
WO 98/40419 or
WO 00/05277. In a further preferred embodiment, the activating compound C) is applied to the
support component B) first and this supported compound is subsequently brought into
contact with the monocyclopentadienyl complex A) of the present invention.
[0046] As support component B), preference is given to using finely divided supports which
can be any organic or inorganic solid. In particular, the support component B) can
be a porous support such as talc, a sheet silicate such as montmorillonite, mica,
an inorganic oxide or a finely divided polymer powder (e.g. polyolefin or a polymer
bearing polar functional groups).
[0047] The support materials used preferably have a specific surface area in the range from
10 to 1000 m
2/g, a pore volume in the range from 0.1 to 5 ml/g and a mean particle size of 1 to
500 µm. Preference is given to supports having a specific surface area in the range
from 50 to 700 m
2/g, a pore volume in the range from 0.4 to 3.5 ml/g and a mean particle size in the
range from 5 to 350 µm. Particular preference is given to supports having a specific
surface area in the range from 200 to 550 m
2/g, a pore volume in the range from 0.5 to 3.0 ml/g and a mean particle size of from
10 to 150 µm.
[0048] The inorganic support can be subjected to a thermal treatment, e.g. to remove adsorbed
water. Such a drying treatment is generally carried out at from 80 to 800°C, preferably
from 100 to 300°C, with drying at from 100 to 200°C preferably being carried out under
reduced pressure and/or under a blanket of inert gas (e.g. nitrogen), or the inorganic
support can be calcined at from 200 to 1 000°C to produce the desired structure of
the solid and/or set the desired OH concentration on the surface. The support can
also be treated chemically using customary desiccants such as metal alkyls, preferably
aluminum alkyls, chlorosilanes or SiCl
4, or else methylaluminoxane. Appropriate treatment methods are described, for example,
in
WO 00/31090.
[0049] The inorganic support material can also be chemically modified. For example, treatment
of silica gel with NH
4SiF
6 or other fluorinating agents leads to fluorination of the silica gel surface, or
treatment of silica gels with silanes containing nitrogen-, fluorine- or sulfur-containing
groups leads to correspondingly modified silica gel surfaces.
[0050] Organic support materials such as finely divided polyolefin powders (e.g. polyethylene,
polypropylene or polystyrene) can also be used and are preferably likewise freed of
adhering moisture, solvent residues or other impurities by appropriate purification
and drying operations before use. It is also possible to use functionalized polymer
supports, e.g. ones based on polystyrene, polyethylene or polypropylene, via whose
functional groups, for example ammonium or hydroxy groups, at least one of the catalyst
components can be fixed.
[0051] Inorganic oxides suitable as support component B) may be found among the oxides of
elements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements.
Examples of oxides preferred as supports include silicon dioxide, aluminum oxide and
mixed oxides of the elements calcium, aluminum, silicon, magnesium or titanium and
also corresponding oxide mixtures. Other inorganic oxides which can be used alone
or in combination with the abovementioned preferred oxidic supports are, for example,
MgO, CaO, AlPO
4, ZrO
2, TiO
2, B
2O
3 or mixtures thereof.
[0052] As solid support materials B) for catalysts for olefin polymerization, preference
is given to using silica gels since particles whose size and structure make them suitable
as supports for olefin polymerization can be produced from this material. Spray-dried
silica gels comprising spherical agglomerates of smaller granular particles, i.e.
primary particles, have been found to be particularly useful. The silica gels can
be dried and/or calcined before use.
[0053] Further preferred supports B) are hydrotalcites and calcined hydrotalcites. In mineralogy,
hydrotalcite is a natural mineral having the ideal formula
Mg
6Al
2(OH)
16CO
3·4H
2O
whose structure is derived from that of brucite Mg(OH)
2. Brucite crystallizes in a sheet structure with the metal ions in octahedral holes
between two layers of close-packed hydroxyl ions, with only every second layer of
the octahedral holes being occupied. In hydrotalcite, some magnesium ions are replaced
by aluminum ions, as a result of which the stack of layers gains a positive charge.
This is compensated by the anions which are located together with water of crystallization
in the layers in between.
[0054] Such sheet structures are found not only in magnesium-aluminum hydroxides, but also
generally in mixed metal hydroxides of the formula
M(II)
2x2+M(III)
23+(OH)4
x+4·A
2/nn-·zH
2O
which have a sheet structure and in which M(II) is a divalent metal such as Mg, Zn,
Cu, Ni, Co, Mn, Ca and/or Fe and M(III) is a trivalent metal such as Al, Fe, Co, Mn,
La, Ce and/or Cr, x is from 0.5 to 10 in steps of 0.5, A is an interstitial anion
and n is the charge on the interstitial anion which can be from 1 to 8, usually from
1 to 4, and z is an integer from 1 to 6, in particular from 2 to 4. Possible interstitial
anions are organic anions such as alkoxide anions, alkyl ether sulfates, aryl ether
sulfates or glycol ether sulfates, inorganic anions such as, in particular, carbonate,
hydrogencarbonate, nitrate, chloride, sulfate or B(OH)
4- or polyoxo metal anions such as Mo
7O
246- or V
10O
286-. However, a mixture of a plurality of such anions can also be present.
[0055] Accordingly, all such mixed metal hydroxides having a sheet structure should be regarded
as hydrotalcites for the purposes of the present invention.
[0056] Calcined hydrotalcites can be prepared from hydrotalcites by calcination, i.e. heating,
by means of which, inter alia, the desired hydroxyl group content can be set. In addition,
the crystal structure also changes. The preparation of the calcined hydrotalcites
used according to the present invention is usually carried out at temperatures above
180°C. Preference is given to calcination for from 3 to 24 hours at from 250°C to
1 000°C, in particular from 400°C to 700°C. It is possible for air or inert gas to
be passed over the solid during calcination or for a vacuum to be applied.
[0057] On heating, the natural or synthetic hydrotalcites firstly give off water, i.e. drying
occurs. On further heating, the actual calcination, the metal hydroxides are converted
into the metal oxides by elimination of hydroxyl groups and interstitial anions; OH
groups or interstitial anions such as carbonate can also still be present in the calcined
hydrotalcites. A measure of this is the loss on ignition. This is the weight loss
experienced by a sample which is heated in two steps firstly for 30 minutes at 200°C
in a drying oven and then for 1 hour at 950°C in a muffle furnace.
[0058] The calcined hydrotalcites used as component B) are thus mixed oxides of the divalent
and trivalent metals M(II) and M(III), with the molar ratio of M(II) to M(III) generally
being in the range from 0.5 to 10, preferably from 0.75 to 8 and in particular from
1 to 4. Furthermore, normal amounts of impurities, for example Si, Fe, Na, Ca or Ti
and also chlorides and sulfates, can also be present.
[0059] Preferred calcined hydrotalcites B) are mixed oxides in which M(II) is magnesium
and M(III) is aluminum. Such aluminum-magnesium mixed oxides are obtainable from Condea
Chemie GmbH (now Sasol Chemie), Hamburg, under the trade name Puralox Mg.
[0060] Preference is also given to calcined hydrotalcites in which the structural transformation
is complete or virtually complete. Calcination, i.e. transformation of the structure,
can be confirmed, for example, by means of X-ray diffraction patterns.
[0061] The hydrotalcites, calcined hydrotalcites or silica gels employed are generally used
as finely divided powders having a mean particle diameter d
50 of from 5 to 200 µm, preferably from 10 to 150 µm, particularly preferably from 15
to 100 µm and in particular from 20 to 70 µm, and usually have pore volumes of from
0.1 to 10 cm
3/g, preferably from 0.2 to 5 cm
3/g, and specific surface areas of from 30 to 1 000 m
2/g, preferably from 50 to 800 m
2/g and in particular from 100 to 600 m
2/g. The monocyclopentadienyl complexes of the present invention are preferably applied
in such an amount that the concentration of transition metal complexes in the finished
catalyst system is from 5 to 200 µmol, preferably from 20 to 100 µmol and particularly
preferably from 25 to 70 µmol per g of support B).
[0062] Some of the monocyclopentadienyl complexes of the present invention have little polymerization
activity on their own and are then brought into contact with an activator, viz. the
component C), to be able to display good polymerization activity. For this reason,
the catalyst system optionally further comprises, as component C), one or more activating
compounds, preferably at least one cation-forming compound C).
[0063] Suitable compounds C) which are able to react with the monocyclopentadienyl complex
A) to convert it into a catalytically active, or more active, compound are, for example,
compounds such as an aluminoxane, a strong uncharged Lewis acid, an ionic compound
having a Lewis-acid cation or an ionic compound containing a Bronsted acid as cation.
[0064] As aluminoxanes, it is possible to use, for example, the compounds described in
WO 00/31090. Particularly useful aluminoxanes are open-chain or cyclic aluminoxane compounds
of the formula (X) or (XI)
- where R1C-R4C
- are each, independently of one another, a C1-C6-alkyl group, preferably a methyl, ethyl, butyl or isobutyl group, and I is an integer
from 1 to 30, preferably from 5 to 25.
[0065] A particularly useful aluminoxane compound is methylaluminoxane.
[0066] These oligomeric aluminoxane compounds are usually prepared by controlled reaction
of a solution of trialkylaluminum with water. In general, the oligomeric aluminoxane
compounds obtained in this way are in the form of mixtures of both linear and cyclic
chain molecules of various lengths, so that I is to be regarded as a mean. The aluminoxane
compounds can also be present in admixture with other metal alkyls, usually aluminum
alkyls. Aluminoxane preparations suitable as component C) are commercially available.
[0067] Furthermore, modified aluminoxanes in which some of the hydrocarbon radicals have
been replaced by hydrogen atoms or alkoxy, aryloxy, siloxy or amide radicals can also
be used as component C) in place of the aluminoxane compounds of the formula (X) or
(XI).
[0068] It has been found to be advantageous to use the monocyclopentadienyl complexes A)
and the aluminoxane compounds in such amounts that the atomic ratio of aluminum from
the aluminoxane compounds including any aluminum alkyl still present to the transition
metal from the monocyclopentadienyl complex A) is in the range from 1:1 to 1 000:1,
preferably from 10:1 to 500:1 and in particular in the range from 20:1 to 400:1.
[0069] A further class of suitable activating components C) are hydroxyaluminoxanes. These
can be prepared, for example, by addition of from 0.5 to 1.2 equivalents of water,
preferably from 0.8 to 1.2 equivalents of water, per equivalent of aluminum to an
alkylaluminum compound, in particular triisobutylaluminum, at low temperatures, usually
below 0°C. Such compounds and their use in olefin polymerization are described, for
example, in
WO 00/24787. The atomic ratio of aluminum from the hydroxyaluminoxane compound to the transition
metal from the monocyclopentadienyl complex A) is usually in the range from 1:1 to
100:1, preferably from 10:1 to 50:1 and in particular in the range from 20:1 to 40:1.
Preference is in this case given to using a monocyclopentadienyl metal dialkyl compound
A).
[0070] As strong, uncharged Lewis acids, preference is given to compounds of the formula
(XII)
M
1CX
1CX
2CX
3C (XII)
where
- M1C
- is an element of group 13 of the Periodic Table of the Elements, in particular B,
Al or Ga, preferably B,
- X1C, X2C and X3C
- are each hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon
atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical or fluorine,
chlorine, bromine or iodine, in particular haloaryls, preferably pentafluorophenyl.
[0071] Further examples of strong, uncharged Lewis acids are given in
WO 00/31090.
[0072] Compounds of this type which are particularly useful as component C) are boranes
and boroxins such as trialkylborane, triarylborane or trimethylboroxin. Particular
preference is given to using boranes which bear at least two perfluorinated aryl radicals.
Particular preference is given to compounds of the formula (XII) in which X
1C, X
2C and X
3C are identical, preferably tris(pentafluorophenyl)borane.
[0073] Suitable compounds C) are preferably prepared by reaction of aluminum or boron compounds
of the formula (XII) with water, alcohols, phenol derivatives, thiophenol derivatives
or aniline derivatives, with halogenated and especially perfluorinated alcohols and
phenols being of particular importance. Examples of particularly useful compounds
are pentafluorophenol, 1,1-bis(pentafluorophenyl)methanol and 4-hydroxy-2,2',3,3',4,4',5,5',6,6'-nonafluorobiphenyl.
Examples of combinations of compounds of the formula (XII) with Bronsted acids are,
in particular, trimethylaluminum/pentafluorophenol, trimethylaluminum/1-bis(pentafluorophenyl)methanol,
trimethylaluminum/4-hydroxy-2,2',3,3',4,4',5,5',6,6'-nonafluorobiphenyl, triethylaluminum/pentafluorophenol
and triisobutylaluminum/pentafluorophenol and triethylaluminum/4,4'-dihydroxy-2,2',3,3',5,5',6,6'-octafluorobiphenyl
hydrate.
[0074] In further suitable aluminum and boron compounds of the formula (XII), X
1C is an OH group. Examples of compounds of this type are boronic acids and borinic
acids, in particular borinic acids having perfluorinated aryl radicals, for example
(C
6F
5)
2BOH.
[0075] Strong uncharged Lewis acids suitable as activating compounds C) also include the
reaction products of a boronic acid with two equivalents of an aluminum trialkyl or
the reaction products of an aluminum trialkyl with two equivalents of an acidic fluorinated,
in particular perfluorinated, hydrocarbon compound such as pentafluorophenol or bis(pentafluorophenyl)borinic
acid.
[0076] Suitable ionic compounds having Lewis acid cations include salt-like compounds of
the cation of the formula (XIII)
[((M
2C)
a+)Q
1Q
2...Q
z]
d+ (XIII)
where
- M2C
- is an element of groups 1 to 16 of the Periodic Table of the Elements,
- Q1 to Q2
- are singly negatively charged groups such as C1-C28-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having from 6 to 20 carbon atoms
in the aryl radical and from 1 to 28 carbon atoms in the alkyl radical, C3-C10-cycloalkyl which may bear C1-C10-alkyl groups as substituents, halogen, C1-C28-alkoxy, C6-C15-aryloxy, silyl or mercaptyl groups,
- a
- is an integer from 1 to 6 and
- z
- is an integer from 0 to 5,
- d
- corresponds to the difference a - z, but d is greater than or equal to 1.
[0077] Particularly useful cations are carbonium cations, oxonium cations and sulfonium
cations and also cationic transition metal complexes. Particular mention may be made
of the triphenylmethyl cation, the silver cation and the 1,1'-dimethylferrocenyl cation.
They preferably have noncoordinating counterions, in particular boron compounds as
are also mentioned in
WO 91/09882, preferably tetrakis(pentafluorophenyl)borate.
[0078] Salts having noncoordinating anions can also be prepared by combining a boron or
aluminum compound, e.g. an aluminum alkyl, with a second compound which can react
to link two or more boron or aluminum atoms, e.g. water, and a third compound which
forms an ionizing ionic compound with the boron or aluminum compound, e.g. triphenylchloromethane,
or optionally a base, preferably an organic nitrogen-containing base, for example
an amine, an aniline derivative or a nitrogen heterocycle. In addition, a fourth compound
which likewise reacts with the boron or aluminum compound, e.g. pentafluorophenol,
can be added.
[0079] Ionic compounds containing Brönsted acids as cations preferably likewise have noncoordinating
counterions. As Brönsted acid, particular preference is given to protonated amine
or aniline derivatives. Preferred cations are N,N-dimethylanilinium, N,N-dimethylcyclohexylammonium
and N,N-dimethylbenzylammonium and also derivatives of the latter two.
[0080] Compounds containing anionic boron heterocycles as are described in
WO 9736937 are also suitable as component C), in particular dimethylanilinium boratabenzene
or trityl boratabenzene.
[0081] Preferred ionic compounds C) comprise borates which bear at least two perfluorinated
aryl radicals. Particular preference is given to N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate
and in particular N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate,
N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate or trityl tetrakispentafluorophenylborate.
[0082] It is also possible for two or more borate anions and/or boranes to be joined to
one another or for a borate anion to be joined to a borane, as in the dianion [(C
6F
5)
3B-C
6F
4-B(C
6F
5)
3]
2 or the anion [(C
6F
5)
3B-CN-B(C
6F
5)
3]
-, or the borate anion can be bound via a bridge bearing a suitable functional group
to the support surface.
[0083] Further suitable activating compounds C) are listed in
WO 00/31090.
[0084] The amount of strong, uncharged Lewis acids, ionic compounds having Lewis-acid cations
or ionic compounds containing Brönsted acids as cations is preferably from 0.1 to
20 equivalents, more preferably from 1 to 10 equivalents, based on the monocyclopentadienyl
complex A).
[0085] Suitable activating compounds C) also include boron-aluminum compounds such as di[bis(pentafluorophenyl)boroxy]methylalane.
Examples of such boron-aluminum compounds are those disclosed in
WO 99/06414.
[0086] It is also possible to use mixtures of all the abovementioned activating compounds
C). Preferred mixtures comprise aluminoxanes, in particular methylaluminoxane, and
an ionic compound, in particular one containing the tetrakis(pentafluorophenyl)borate
anion, and/or a strong uncharged Lewis acid, in particular tris(pentafluorophenyl)borane.
[0087] Both the monocyclopentadienyl complexes A) and the activating compounds C) are preferably
used in a solvent, preferably an aromatic hydrocarbon having from 6 to 20 carbon atoms,
in particular xylenes, toluene, pentane, hexane, heptane or a mixture thereof.
[0088] A further possibility is to use an activating compound C) which can simultaneously
be employed as support B). Such systems are obtained, for example, from an inorganic
oxide by treatment with zirconium alkoxide and subsequent chlorination, for example
by means of carbon tetrachloride. The preparation of such systems is described, for
example, in
WO 01/41920.
[0089] A likewise broad product spectrum can be achieved by use of the monocyclopentadienyl
complexes A) of the present invention in combination with at least one further catalyst
D) which is suitable for the polymerization of olefins. It is therefore possible to
use one or more catalysts suitable for olefin polymerization as optional component
D) in the catalyst system. Possible catalysts D) are, in particular, classical Ziegler-Natta
catalysts based on titanium and classical Phillips catalysts based on chromium oxides.
[0090] Possible components D) are in principle all compounds of transition metals of groups
3 to 12 of the Periodic Table or the lanthanides which contain organic groups and
preferably form active catalysts for olefin polymerization after reaction with the
components C) in the presence of A) and optionally B) and/or E). These are usually
compounds in which at least one monodentate or polydentate ligand is bound to the
central atom via a sigma or pi bond. Possible ligands include both ligands containing
cyclopentadienyl groups and ligands which are free of cyclopentadienyl groups. A large
number of such compounds B) suitable for olefin polymerization are described in
Chem. Rev. 2000, Vol, 100, No. 4. Furthermore, multinuclear cyclopentadienyl complexes are also suitable for olefin
polymerization.
[0091] Particularly well-suited components D) include compounds having at least one cyclopentadienyl
ligand, which are generally referred to as metallocene complexes. Particularly useful
metallocene complexes are those of the formula (XIV)
where the substituents and indices have the following meanings:
- M1D
- is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum
or tungsten, or an element of group 3 of the Periodic Table and the lanthanides,
- XD
- is fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C2-C10-alkenyl, C6-C15-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6
to 20 carbon atoms in the aryl radical, -OR6D or -NR6DR7D, or two radicals XD form a substituted or unsubstituted diene ligand, in particular a 1,3-diene ligand,
and the radicals XD are identical or different and may be joined to one another,
- E1D-E5D
- are each carbon or not more than one E1D to E5D is phosphorus or nitrogen, preferably carbon,
- t
- is 1, 2 or 3 and is such that, depending on the valence of M1D, the metallocene complex of the formula (XIV) is uncharged,
where
- R6D and R7D
- are each C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon
atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical and
- R1D to R5D
- are each, independently of one another, C1-C22-alkyl, 5-to 7-membered cycloalkyl or cycloalkenyl which may in turn bear C1-C10-alkyl groups as substituents, C2-C22-alkenyl, C6-C22-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl radical and from 6
to 21 carbon atoms in the aryl radical, NR8D2, N(SiR8D3)2, OR8D, OSiR8D3, SiR8D3, where the organic radicals R1D-R5D may also be substituted by halogens and/or two radicals R1D-R5D, in particular vicinal radicals, may also be joined to form a five- six- or seven-membered
ring, and/or two vicinal radicals R1D-R5D may be joined to form a five-, six- or seven-membered heterocycle which contains
at least one atom from the group consisting of N, P, O and S, where
- the radicals R8D
- can be identical or different and are each C1-C10-alkyl, C3-C10-cycloalkyl, C6-C15-aryl, C1-C4-alkoxy or C6-C10-aryloxy and
- Z1D
- is defined as for XD or is
where the radicals
- R9D to R13D
- are each, independently of one another, hydrogen, C1-C22-alkyl, 5- to 7-membered cycloalkyl or cycloalkenyl which may in turn bear C1-C10-alkyl groups as substituents, C2-C22-alkenyl, C6-C22-aryl, arylalkyl having from 1 to 16 carbon atoms in the alkyl radical and 6-21 carbon
atoms in the aryl radical, NR14D2, N(SiR14D3)2, OR14D, OSiR14D3, SiR14D3, where the organic radicals R9D-R13D may also be substituted by halogens and/or two radicals R9D-R13D, in particular vicinal radicals, may also be joined to form a five-, six- or seven-membered
ring, and/or two vicinal radicals R9D-R13D may be joined to form a five-, six- or seven-membered heterocycle which contains
at least one atom from the group consisting of N, P, O and S, where
- the radicals R14D
- are identical or different and are each C1-C10-alkyl, C3-C10-cycloalkyl, C6-C15-aryl, C1-C4-alkoxy or C6-C10-aryloxy,
- E6D-E10D
- are each carbon or not more than one E6D to E10D is phosphorus or nitrogen, preferably carbon,
[0092] or the radicals R
4D and Z
1D together form an -R
15Dv-A
1D- group in which
- R15D
- is
=BR16D,= BNR16DR17D, =AIR16D, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR16D, =CO, =PR16D or =P(O)R16D,
where
- R16D-R21D
- are identical or different and are each a hydrogen atom, a halogen atom, a trimethylsilyl
group, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-fluoroaryl group, a C6-C10-aryl group, a C1-C10-alkoxy group, a C7-C15-alkylaryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group or two adjacent radicals together with the atoms connecting them
form a saturated or unsaturated ring having from 4 to 15 carbon atoms, and
- M2D-M4D
- are each silicon, germanium or tin, preferably silicon,
- A1D
- is
-NR22D2, -PR22D2 or an unsubstituted, substituted or fused heterocyclic ring system, where
- the radicals R22D
- are each, independently of one another, C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl, C7-C18-alkylaryl or Si(R23D)3,
- R23D
- is hydrogen, C1-C10-alkyl, C6-C15-aryl which may in turn bear C1-C4-alkyl groups as substituents or C3-C10-cycloalkyl,
- v
- is 1 or when A1D is an unsubstituted, substituted or fused heterocyclic ring system may also be 0,
or the radicals R
4D and R
12D together form a -R
15D- group.
[0093] A
1D together with the bridge R
15D can, for example, form an amine, ether, thioether or phosphine. However, A
1D may also be an unsubstituted, substituted or fused heterocyclic aromatic ring system
which can contain heteroatoms from the group consisting of oxygen, sulfur, nitrogen
and phosphorus in addition to carbon atoms in the ring. Examples of five-membered
heteroaryl groups which can contain from one to four nitrogen atoms and/or a sulfur
or oxygen atom as ring atoms in addition to carbon atoms are 2-furyl, 2-thienyl, 2-pyrrolyl,
3-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 5-isothiazolyl, 1-pyrazolyl, 3-pyrazolyl,
5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl,
2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,
1,3,4-oxadiazol-2-yl or 1,2,4-triazol-3-yl. Examples of 6-membered heteroaryl groups,
which can contain from one to four nitrogen atoms and/or a phosphorus atom, are 2-pyridinyl,
2-phosphaphenyl, 3-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl
and 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl and 1,2,4-triazin-6-yl. The 5-membered
and 6-membered heteroaryl groups can also be substituted by C
1-C
10-alkyl, C
6-C
10-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-10 carbon
atoms in the aryl radical, trialkylsilyl or halogens such as fluorine, chlorine or
bromine or be fused with one or more aromatics or heteroaromatics. Examples of benzo-fused
5-membered heteroaryl groups are 2-indolyl, 7-indolyl, 2-coumaronyl, 7-coumaronyl,
2-thianaphthenyl, 7-thianaphthenyl, 3-indazolyl, 7-indazolyl, 2-benzimidazolyl and
7-benzimidazolyl. Examples of benzo-fused 6-membered heteroaryl groups are 2-quinolyl,
8-quinolyl, 3-cinnolyl, 8-cinnolyl, 1-phthalazyl, 2-quinazolyl, 4-quinazolyl, 8-quinazolyl,
5-quinoxalyl, 4-acridyl, 1-phenanthridyl and 1-phenazyl. Naming and numbering of the
heterocycles has been taken from
L. Fieser and M. Fieser, Lehrbuch der organischen Chemie, 3rd revised edition, Verlag
Chemie, Weinheim 1957.
[0094] It is preferred that the radicals X
D in the formula (XIV) are identical, preferably fluorine, chlorine, bromine, C
1-C
7-alkyl or aralkyl, in particular chlorine, methyl or benzyl.
[0095] The synthesis of such complexes can be carried out by methods known per se, preferably
by reaction of the appropriately substituted, cyclic hydrocarbon anions with halides
of titanium, zirconium, hafnium or chromium.
[0097] Among the compounds of the formula (XIVa), particular preference is given to those
in which
- M1D
- is titanium, vanadium or chromium,
- XD
- is chlorine, C1-C4-alkyl, phenyl, alkoxy or aryloxy,
- t
- is 1 or 2 and
- R1D to R5D
- are each hydrogen, C1-C6-alkyl or two adjacent radicals R1D to R5D form a substituted or unsubstituted benzo group.
[0098] Among the compounds of the formula (XIVb), preference is given to those in which
- M1D
- is titanium, zirconium, vanadium, hafnium or chromium,
- XD
- is fluorine, chlorine, C1-C4-alkyl or benzyl, or two radicals XD form a substituted or unsubstituted butadiene ligand,
- t
- is 0 in the case of chromium, otherwise 1 or 2, preferably 2,
- R1D to R5D
- are each hydrogen, C1-C8-alkyl, C6-C8-aryl, NR8D2, OSiR8D3 or Si(R8D)3 and
- R9D to R13D
- are each hydrogen, C1-C8-alkyl or C6-C8-aryl, NR14D2, OSiR14D3 or Si(R14D)3
or two radicals
R1D to R
5D and/or R
9D to R
1D together with the C
5 ring form an indenyl, fluorenyl or substituted indenyl or fluorenyl system.
[0099] The compounds of the formula (XIVb) in which the cyclopentadienyl radicals are identical
are particularly useful.
[0100] Examples of particularly useful compounds D) of the formula (XIVb) include: bis(cyclopentadienyl)chromium,
bis(indenyl)titanium dichloride, bis(fluorenyl)titanium dichloride, bis(tetrahydroindenyl)titanium
dichloride, bis(pentamethylcyclopentadienyl)titanium dichloride, bis(trimethylsilylcyclopentadienyl)titanium
dichloride, bis(trimethoxysilylcyclopentadienyl)titanium dichloride, bis(isobutylcyclopentadienyl)titanium
dichloride, bis(3-butenylcyclopentadienyl)titanium dichloride, bis(methylcyclopentadienyl)titanium
dichloride, bis(1-,3-di-tert-butylcyclopentadienyl)titanium dichloride, bis(trifluoromethylcyclopentadienyl)titanium
dichloride, bis(tert-butylcyclopentadienyl)titanium dichloride, bis(n-butylcyclopentadienyl)titanium
dichloride, bis(phenylcyclopentadienyl)titanium dichloride, bis(N,N-dimethylaminomethylcyclopentadienyl)-titanium
dichloride, bis(1,3-dimethylcyclopentadienyl)titanium dichloride, bis(1-methyl-3-n-butyl-cyclopentadienyl)titanium
dichloride, (cyclopentadienyl)(methylcyclopentadienyl)titanium dichloride, (cyclopentadienyl)(n-butylcyclopentadienyl)titanium
dichloride, (methylcyclopentadienyl)(n-butylcyclopentadienyl)titanium dichloride,
(cyclopentadienyl)(1-methyl-3-n-butylcyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)zirconium
dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium
dichloride, bis(ethylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium
dichloride, bis(tert-butylcyclopentadienyl)zirconium dichloride, bis(isobutylcyclopentadienyl)zirconium
dichloride, bis(3-butenylcyclopentadienyl)zirconium dichloride, bis(trifluoromethylcyclopentadienyl)zirconium
dichloride, bis(phenylcyclopentadienyl)zirconium dichloride, bis-(1,3-dimethylcyclopentadienyl)zirconium
dichloride, bis(1-n-butyl-3-methylcyclopentadienyl)-zirconium dichloride, bis(1,3-ditert-butylcyclopentadienyl)zirconium
dichloride, bis(tetramethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium
dichloride, bis(tetrahydroindenyl)-zirconium dichloride, bis(fluorenyl)zirconium dichloride,
(cyclopentadienyl)(methylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(n-butylcyclopentadienyl)zirconium
dichloride, (methylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride,
(cyclopentadienyl)(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, bis(trimethoxysilylcyclopentadienyl)zirconium
dichloride and bis(trimethylsilylcyclopentadienyl)-zirconium dichloride, and also
the corresponding dimethylzirconium compounds.
[0101] Particularly useful compounds of the formula (XIVc) are those in which
- R15D
- is
or = BR16D or = BNR16DR17D ,
- M1D
- is titanium, zirconium or hafnium, in particular zirconium, and
- the radicals XD
- are identical or different and are each chlorine, C1-C4-alkyl, benzyl, phenyl or C7-C15-alkylaryloxy.
[0102] Particularly useful compounds of the formula (XVIc) are those of the formula (XVIc')
where
the radicals R' are identical or different and are each hydrogen, C1-C10-alkyl or C3-C10-cycloalkyl, preferably methyl, ethyl, isopropyl or cyclohexyl, C6-C20-aryl, preferably phenyl, naphthyl or mesityl, C7-C40-arylalkyl, C7-C40-alkylaryl, preferably 4-tert-butylphenyl or 3,5-di-tert-butylphenyl, or C8-C40-arylalkenyl,
R5D and R13D are identical or different and are each hydrogen, C1-C6-alkyl, preferably methyl, ethyl, isopropyl, n-propyl, n-butyl, n-hexyl or tert-butyl,
And the rings S and T are identical or different and saturated, unsaturated or partially
saturated.
[0103] The indenyl or tetrahydroindenyl ligands of the metallocenes of the formula (XIVc')
are preferably substituted in the 2 position, the 2,4 positions, the 4,7 positions,
the 2,4,7 positions, the 2,6 positions, the 2,4,6 positions, the 2,5,6 positions,
the 2,4,5,6 positions or the 2,4,5,6,7 positions, in particular in the 2,4 positions,
with the following numbering applying to the site of substitution:
[0104] Furthermore, preference is given to using bridged bis-indenyl complexes in the rac
or pseudo-rac form as component D). The term "pseudo-rac form" refers to complexes
in which the two indenyl ligands are in the rac arrangement relative to one another
when all other substituents of the complex are disregarded.
[0105] Further examples of particularly useful catalysts D) (XIVc) and (XIVc') include:
methylenebis(cyclopentadienyl)zirconium dichloride, methylenebis(3-methylcyclopentadienyl)-zirconium
dichloride, methylenebis(3-n-butylcyclopentadienyl)zirconium dichloride, methylenebis(indenyl)zirconium
dichloride, methylenebis(tetrahydroindenyl)zirconium dichloride, isopropylidenebis(cyclopentadienyl)zirconium
dichloride, isopropylidenebis(3-trimethylsilylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(3-methylcyclopentadienyl)zirconium dichloride, isopropylidenebis(3-n-butylcyclopentadienyl)zirconium
dichloride, isopropylidenebis(3-phenylcyclopentadienyl)zirconium dichloride, isopropylidenebis(indenyl)zirconium
dichloride, isopropylidenebis(tetrahydroindenyl)zirconium dichloride, dimethylsilanediylbis(cyclopentadienyl)zirconium
dichloride, dimethylsilanediylbis(indenyl)zirconium dichloride, dimethylsilanediylbis(tetrahydroindenyl)zirconium
dichloride, ethylenebis(cyclopentadienyl)-zirconium dichloride, ethylenebis(indenyl)zirconium
dichloride, ethylenebis(tetrahydroindenyl)-zirconium dichloride,tetramethylethylene-9-fluorenylcyclopentadienylzirconium
dichloride, dimethylsilanediylbis(tetramethylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(3-trimethylsilylcyclopentadienyl)zirconium dichloride, dimethylsilanediylbis(3-methylcyclopentadienyl)zirconium
dichloride, dimethylsilanediylbis(3-n-butylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(3-tert-butyl-5-methylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(3-tert-butyl-5-ethylcyclopentadienyl)zirconium dichloride, dimethylsilanediylbis(2-methylindenyl)zirconium
dichloride, dimethylsilanediylbis(2-isopropylindenyl)zirconium dichloride, dimethylsilanediylbis(2-tert-butylindenyl)zirconium
dichloride, diethylsilanediylbis(2-methylindenyl)zirconium dibromide, dimethylsilanediylbis(3-methyl-5-methylcyclopentadienyl)zirconium
dichloride, dimethylsilanediylbis(3-ethyl-5-isopropylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2-ethylindenyl)zirconium dichloride, dimethylsilanediylbis(2-methyl-4,5-benzindenyl)zirconium
dichloride, dimethylsilanediylbis(2-ethyl-4,5-benzindenyl)zirconium dichloride, methylphenylsilanediylbis(2-methyl-4,5-benzindenyl)zirconium
dichloride, methylphenylsilanediylbis(2-ethyl-4,5-benzindenyl)zirconium dichloride,
diphenylsilanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride, diphenylsilanediylbis(2-ethyl-4,5-benzindenyl)zirconium
dichloride, diphenylsilanediylbis(2-methylindenyl)hafnium dichloride, dimethylsilanediylbis(2-methyl-4-phenylindenyl)zirconium
dichloride, dimethylsilanediylbis(2-ethyl-4-phenylindenyl)-zirconium dichloride, dimethylsilanediylbis(2-methyl-4-(1-naphthyl)indenyl)zirconium
dichloride, dimethylsilanediylbis(2-ethyl-4-(1-naphthyl)indenyl)zirconium dichloride,
dimethylsilanediylbis(2-propyl-4-(1-naphthyl)indenyl)zirconium dichloride, dimethylsilanediylbis(2-i-butyl-4-(1-naphthyl)indenyl)zirconium
dichloride, dimethylsilanediylbis(2-propyl-4-(9-phenanthryl)indenyl)zirconium dichloride,
dimethylsilanediylbis(2-methyl-4-isopropylindenyl)zirconium dichloride, dimethylsilanediylbis(2,7-dimethyl-4-isopropylindenyl)zirconium
dichloride, dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)zirconium dichloride,
dimethylsilanediylbis(2-methyl-4[p-trifluoromethylphenyl]-indenyl)zirconium dichloride,
dimethylsilanediylbis(2-methyl-4-[3',5'-dimethylphenyl]indenyl)zirconium dichloride,
dimethylsilanediylbis(2-methyl-4.-[4'-tert-butylphenyl]indenyl)zirconium dichloride,
diethylsilanediylbis(2-methyl-4-[4'-tert-butylphenyl]indenyl)zirconium dichloride,
dimethylsilanediylbis(2-ethyl-4-[4'-tert-butylphenyl]indenyl)zirconium dichloride,
dimethylsilanediylbis(2-propyl-4-[4'-tert-butylphenyl]indenyl)zirconium dichloride,
dimethylsilanediylbis(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)zirconium dichloride,
dimethylsilanediylbis(2-n-butyl-4-[4'-tert-butylphenyl]indenyl)zirconium dichloride,
dimethylsilanediylbis(2-hexyl-4-[4'-tert-butyl-phenyl]indenyl)-zirconium dichloride,
dimethylsilanediyl(2-isopropyl-4-phenylindenyl)-(2-methyl-4-phenylindenyl)zirconium
dichloride, dimethylsilanediyl(2-isopropyl-4-(1-naphthyl)indenyl)-(2-methyl-4-(1-naphthyl)indenyl)zirconium
dichloride, dimethylsilanediyl(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)-(2-methyl-4-[4'-tert-butylphenyl]indenyl)zirconium
dichloride, dimethylsilanediyl(2-isopropyl-4.-[4'-tert-butylphenyl]indenyl)-(2-ethyl-4-[4'-tert-butylphenyl]indenyl)zirconium
dichloride, dimethylsilanediyl(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)-(2-methyl-4-[3',5'-bis-tert-butylphenyl]indenyl)zirconium
dichloride, dimethylsilanediyl(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)-(2-methyl-4-[1'-naphthyl]indenyl)-zirconium
dichloride and ethylene(2-isopropyl-4-[4'-tert-butylphenyl]indenyl)-(2-methyl-4-[4'-tert-butylphenyl]indenyl)zirconium
dichloride, and also the corresponding dimethylzirconium, monochloromono(alkylaryloxy)zirconium
and di(alkylaryloxy)zirconium compounds. The complexes are preferably used in the
rac form.
[0106] Such complexes can be synthesized by methods known per se, preferably by reacting
the appropriately substituted, cyclic hydrocarbon anions with halides of titanium,
zirconium, hafnium, vanadium, niobium, tantalum or chromium. Examples of appropriate
preparative methods are described, inter alia, in the
Journal of Organometallic Chemistry, 369 (1989), 359-370.
[0107] Particularly useful compounds of the formula (XIVd) are those in which
- M1D
- is titanium or zirconium, in particular titanium, and
- XD
- is chlorine, C1-C4-alkyl or phenyl or two radicals XD form a substituted or unsubstituted butadiene ligand,
- R15D
- is
or = BR
16D or = BNR
16DR
17D,
- A1D
- is
- t
- is 1 or 2, preferably 2,
- R1D to R3D and R5D
- are each hydrogen, C1-C10-alkyl, preferably methyl, C3-C10-cycloalkyl, C6-C15-aryl, NR8D2 or Si(R8D)3, or two adjacent radicals form a cyclic group having from 4 to 12 carbon atoms, with
particular preference being given to all R1D to R3D and R5D being methyl.
[0108] Particularly useful complexes D) of the formula (XIVd) are dimethylsilanediyl(tetramethylcyclopentadienyl)(phenylamino)titanium
dichloride, dimethylsilanediyl(tetramethylcyclopentadienyl)(benzylamino)titanium dichloride,
dimethylsilanediyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride,
dimethylsilanediyl(tetramethylcyclopentadienyl)(adamantyl)titanium dichloride and
dimethylsilanediyl(indenyl)(tert-butylamino)titanium dichloride.
[0109] Another group of compounds of the formula (XIVd) which are particularly useful are
those in which
- M1D
- is titanium, vanadium or chromium, preferably in the oxidation state III, and
- XD
- is chlorine, C1-C4-alkyl or phenyl or two radicals XD form a substituted or unsubstituted butadiene ligand,
- R15D
- is
or
- A1D
- is -O-R22D, - NR22D2, - PR22D2 or an unsubstituted, substituted or fused, heterocyclic, in particular heteroaromatic,
ring system,
- v
- is 1 or when A1D is an unsubstituted, substituted or fused, heterocyclic ring system may be 0 or 1
and
- R1D to R3D and R5D
- are each hydrogen, C1-C10-alkyl, C3-C10-cycloalkyl, C6-C15-aryl or Si(R8D)3, or two adjacent radicals form a cyclic group having from 4 to 12 carbon atoms.
[0110] In a preferred embodiment, A
1D is an unsubstituted, substituted or fused, heteroaromatic ring system and M
1D is chromium. Very particular preference is given to A
1D being an unsubstituted or substituted, e.g. alkyl-substituted, in particular substituted
or unsubstituted quinolyl or pyridyl bound in position 8 or 2, e.g. 8-quinolyl, 8-(2-methylquinolyl),
8-(2,3,4-trimethylquinolyl), 8-(2,3,4,5,6,7-hexamethylquinolyl), v being 0 and M
1D being chromium. Preferred catalysts D) of this type are 1-(8-quinolyl)-2-methyl-4-methylcyclopentadienylchromium(III)
dichloride, 1-(8-quinolyl)-3-isopropyl-5-methylcyclopentadienylchromium(III) dichloride,
1-(8-quinolyl)-3-tert-butyl-5-methylcyclopentadienylchromium(III) dichloride, 1-(8-quinolyl)-2,3,4,5-tetramethylcyclopentadienylchromium(III)
dichloride, 1-(8-quinolyl)tetrahydroindenylchromium(III) dichloride, 1-(8-quinolyl)indenylchromium(III)
dichloride, 1-(8-quinolyl)-2-methylindenylchromium(III) dichloride, 1-(8-quinolyl)-2-isopropylindenylchromium(III)
dichloride, 1-(8-quinolyl)-2-ethylindenylchromium(III) dichloride, 1-(8-quinolyl)-2-tert-butylindenylchromium(III)
dichloride, 1-(8-quinolyl)benzindenylchromium(III) dichloride, 1-(8-quinolyl)-2-methylbenzindenylchromium(III)
dichloride, 1-(8-(2-methylquinolyl))-2-methyl-4-methylcyclopentadienylchromium(III)
dichloride, 1-(8-(2-methylquinolyl))-2,3,4,5-tetramethylcyclopentadienylchromium(III)
dichloride, 1-(8-(2-methylquinolyl))-tetrahydroindenylchromium(III) dichloride, 1-(8-(2-methylquinolyl))indenylchromium(III)
dichloride, 1-(8-(2-methylquinolyl))-2-methylindenylchromium(III) dichloride, 1-(8-(2-methylquinolyl))-2-isopropylindenylchromium(III)
dichloride, 1-(8-(2-methylquinolyl))-2-ethylindenylchromium(III) dichloride, 1-(8-(2-methylquinolyl))-2-tert-butylindenylchromium(III)
dichloride, 1-(8-(2-methylquinolyl))benzindenylchromium(III) dichloride, 1-(2-pyridylmethyl)indenylchromium(III)
dichloride or 1-(8-(2-methylquinolyl))-2-methylbenzindenylchromium(III) dichloride.
[0111] Furthermore, owing to the ease of preparation, preference is given to compounds in
which R
15D is CH=CH or 1,2-phenylene and A
1D is NR
22D2, and compounds in which R
15D is CH
2, C(CH
3)
2 or Si(CH
3)
2 and A
1D is unsubstituted or substituted 2- or 8-quinolyl or unsubstituted or substituted
2-pyridyl.
[0113] The metal complexes, in particular the chromium complexes, can be obtained in a simple
manner by reacting the appropriate metal salts, e.g. metal chlorides, with the ligand
anion (e.g. using methods analogous to the examples in
DE-A-19710615).
[0114] Further suitable catalysts D) include metallocenes having at least one ligand which
is formed from a cyclopentadienyl or heterocyclopentadienyl and a fused-on heterocycle,
with the heterocycles preferably being aromatic and containing nitrogen and/or sulfur.
Such compounds are described, for example, in
WO 98/22486. These are in particular dimethylsilanediyl(2-methyl-4-phenylindenyl)(2,5-dimethyl-N-phenyl-4-azapentalene)zirconium
dichloride, dimethylsilanediylbis(2-methyl-4-phenyl-4-hydroazulenyl)zirconium dichloride,
dimethylsilanediylbis(2-ethyl-4-phenyl-4-hydroazulenyl)zirconium dichloride, bis(2,5-dimethyl-n-phenyl-4-azapentalene)zirconium
dichloride or (indenyl)(2,5-dimethyl-N-phenyl-4-azapentalene)zirconium dichloride.
[0115] Further suitable catalysts D) are systems in which a metallocene compound is combined
with, for example, an inorganic oxide which has been treated with zirconium alkoxide
and subsequently chlorinated, for example by means of carbon tetrachloride. The preparation
of such systems is described, for example, in
WO 01/41920.
[0116] Other suitable catalysts D) include imidochromium compounds in which chromium bears
at least one imido group as structural feature. These compounds and their preparation
are described, for example, in
WO 01/09148.
[0117] Further suitable components D) include transition metal complexes with a tridentate
macrocyclic ligand, in particular substituted and unsubstituted 1,3,5-triazacyclohexanes
and 1,4,7-triazacyclononanes. In the case of this type of catalyst, preference is
likewise given to chromium complexes. Preferred catalysts of this type are [1,3,5-tri(methyl)-1,3,5-triazacyclohexane]chromium
trichloride, [1,3,5-tri(ethyl)-1,3,5-triazacyclohexane]chromium trichloride, [1,3,5-tri(octyl)-1,3,5-triazacyclohexane]chromium
trichloride, [1,3,5-tri(dodecyl)-1,3,5-triazacyclohexane]chromium trichloride and
[1,3,5-tri(benzyl)-1,3,5-triazacyclohexane]chromium trichloride.
[0118] Further suitable catalysts D) are, for example, transition metal complexes with at
least one ligand of the formulae XV to XIX,
where the transition metal is selected from among the elements Ti, Zr, Hf, Sc, V,
Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pd, Pt and the elements of the rare earth metals. Preference
is given to compounds having nickel, iron, cobalt or palladium as central metal.
[0119] E
F is an element of group 15 of the Periodic Table of the Elements, preferably N or
P, with particular preference being given to N. The two or three atoms E
F in a molecule can be identical or different.
[0120] The radicals R
1F to R
25F, which may be identical or different within a ligand system XV to XIX, are as follows:
- R1F and R4F
- are each, independently of one another, a hydrocarbon radical or a substituted hydrocarbon
radical, preferably a hydrocarbon radical in which the carbon atom adjacent to the
element EF is bound to at least two carbon atoms,
- R2F and R3F
- are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted
hydrocarbon radical, where R2F and R3F may together also form a ring system in which one or more heteroatoms may also be
present,
- R6F and R8F
- are each, independently of one another, a hydrocarbon radical or a substituted hydrocarbon
radical,
- R5F and R9F
- are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted
hydrocarbon radical,
where R
6F and R
5F or R
8F and R
9F may together also form a ring system,
- R7F
- the radicals R7F are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted
hydrocarbon radical, where two R7F may together also form a ring system,
- R10F and R14F
- are each, independently of one another, a hydrocarbon radical or a substituted hydrocarbon
radical,
- R11F, R12F, R12F' and R13F
- are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted
hydrocarbon radical, where two or more geminal or vicinal radicals R11A, R12A, R12A, and R13A may together also form a ring system,
- R15F and R18F
- are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted
hydrocarbon radical,
- R16F and R17F
- are each, independently of one another, hydrogen, a hydrocarbon radical or a substituted
hydrocarbon radical,
- R19F and R25F
- are each, independently of one another, C2-C20-alkenyl, C6-C20-aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon
atoms in the aryl radical, where the organic radicals R19F and R25F may also be substituted by halogens,
- R20F-R24F
- are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon
atoms in the aryl radical or SiR26F3, where the organic radicals R20F-R24F may also be substituted by halogens and two vicinal radicals R20F-R24F may also be joined to form a five- or six-membered ring and
- R26F
- the radicals R26F are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20
carbon atoms in the aryl radical and two radicals R26F may also be joined to form a five- or six-membered ring,
- x
- is 0 or 1, with the complex of the formula (XVI) being negatively charged when x is
0, and
- y
- is an integer from 1 to 4, preferably 2 or 3.
[0121] Particularly useful transition metal complexes are those having Fe, Co, Ni, Pd or
Pt as central metal and containing ligands of the formula (XV). Particular preference
is given to diimine complexes of Ni or Pd, e.g.:
[0122] Di(2,6-di-i-propylphenyl)-2,3-dimethyldiazabutadienepalladium dichloride, di(di-i-propylphenyl)-2,3-dimethyldiazabutadienenickel
dichloride, di(2,6-di-i-propylphenyl)dimethyldiazabutadienedimethylpalladium, di(2,6-di-i-propylphenyl)-2,3-dimethyldiazabutadienedimethylnickel,
di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienepalladium dichloride, di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienenickel
dichloride, di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienedimethylpalladium, di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienedimethylnickel,
di(2-methylphenyl)-2,3-dimethyldiazabutadienepalladium dichloride, di(2-methylphenyl)-2,3-dimethyldiazabutadienenickel
dichloride, di(2-methylphenyl)-2,3-dimethyldiazabutadienedimethylpalladium, di(2-methylphenyl)-2,3-dimethyldiazabutadienedimethylnickel,
diphenyl-2,3-dimethyldiazabutadienepalladium dichloride, diphenyl-2,3-dimethyldiazabutadienenickel
dichloride, diphenyl-2,3-dimethyldiazabutadienedimethylpalladium, diphenyl-2,3-dimethyldiazabutadienedimethylnickel,
di(2,6-dimethylphenyl)azanaphthenepalladium dichloride, di(2,6-dimethylphenyl)azanaphthenenickel
dichloride, di(2,6-dimethylphenyl)azanaphthenedimethylpalladium, di(2,6-dimethylphenyl)azanaphthenedimethylnickel,
1,1'-bipyridylpalladium dichloride, 1,1'-bipyridylnickel dichloride, 1,1'-bipyridyl(dimethyl)palladium,
1,1 '-bipyridyl(dimethyl)nickel.
[0123] Particularly useful compounds (XIX) also include those which are described in
J. Am. Chem. Soc. 120, p. 4049 ff. (1998),
J. Chem. Soc., Chem. Commun. 1998, 849, and
WO 98/27124. E
F is preferably nitrogen and R
19F and R
25F in (XIX) are preferably phenyl, naphthyl, biphenyl, anthranyl, o-, m-, p-methylphenyl,
2,3-, 2,4-, 2,5- or 2,6-dimethylphenyl, -dichlorophenyl or -dibromophenyl, 2-chloro-6-methylphenyl,
2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trimethylphenyl, in particular 2,3-
or 2,6-dimethylphenyl, -diisopropylphenyl, -dichlorophenyl or -dibromophenyl and 2,4,6-trimethylphenyl.
At the same time, R
20F and R
24F are preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl,
n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl or phenyl, in particular hydrogen or
methyl. R
21F and R
23F are preferably hydrogen and R
22F is preferably hydrogen, methyl, ethyl or phenyl, in particular hydrogen. Preference
is given to complexes of the ligands F-XIX with the transition metals Fe, Co or Ni,
in particular Fe. Particular preference is given to 2,6-diacetylpyridinebis(2,4-dimethylphenylimine)iron
dichloride, 2,6-diacetylpyridinebis(2,4,6-trimethylphenylimine)iron dichloride, 2,6-diacetylpyridinebis(2-chloro-6-methylphenylimine)iron
dichloride, 2,6-diacetylpyridinebis(2,6-diisopropylphenylimine)iron dichloride, 2,6-diacetylpyridinebis(2,6-dichlorophenylimine)iron
dichloride, 2,6-pyridinedicarboxaldehydebis(2,6-diisopropylphenylimine)iron dichloride,
2,6-diacetylpyridinebis(2,4-dimethylphenylimine)cobalt dichloride, 2,6-diacetylpyridinebis(2,4,6-trimethylphenylimine)cobalt
dichloride, 2,6-diacetylpyridinebis(2-chloro-6-methylphenylimine)cobalt dichloride,
2,6-diacetylpyridinebis(2,6-diisopropylphenylimine)cobalt dichloride, 2,6-diacetylpyridinebis(2,6-dichlorophenylimine)cobalt
dichloride, and 2,6-pyridinedicarboxaldehydebis(2,6-diisopropylphenylimine)cobalt
dichloride.
[0124] Iminophenoxide complexes can also be used as catalysts D). The ligands of these complexes
can be prepared, for example, from substituted or unsubstituted salicylaldehydes and
primary amines, in particular substituted or unsubstituted arylamines. Transition
metal complexes with pi ligands having one or more heteroatoms in the pi system, for
example the boratabenzene ligand, the pyrrolyl anion or the phospholyl anion, can
also be used as catalysts D).
[0125] Further complexes suitable as catalysts D) include those which have bidentate or
tridentate chelating ligands. In such ligands, for example, an ether function is linked
to an amine or amide function or an amide is linked to a heteroaromatic such as pyridine.
[0126] Such combinations of components A) and D) enable, for example, bimodal products to
be prepared or comonomers to be generated in situ. Preference is given to using at
least one monocyclopentadienyl complex A) in the presence of at least one further
catalyst D) customary for the polymerization of olefins and if desired, one or more
activating compounds C). Here, depending on the catalyst combinations A) and D), one
or more activating compounds C) may be advantageous. The polymerization catalysts
D) can likewise be supported and can be used simultaneously or in any order with the
complex A) of the present invention. For example, the monocyclopentadienyl complex
A) and the polymerization catalysts D) can be applied together to a support B) or
different supports B). It is also possible to use mixtures of various catalysts as
component D). The molar ratio of transition metal complex A) to polymerization catalyst
D) is usually in the range from 1:100 to 100:1, preferably from 1:10 to 20:1 and particularly
preferably from 1:1 to 10:1.
[0127] The catalyst system may further comprise, as additional component E), a metal compound
of the formula (XX),
M
G(R
1G)
rG(R
2G)
sG(R
3G)
tG (XX)
where
- MG
- is Li, Na, K, Be, Mg, Ca, Sr, Ba, boron, aluminum, gallium, indium, thallium, zinc,
in particular Li, Na, K, Mg, boron, aluminum or Zn,
- R1G
- is hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl or arylalkyl each having from 1 to 10 carbon atoms in the alkyl radical
and from 6 to 20 carbon atoms in the aryl radical,
- R2G and R3G
- are each hydrogen, halogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl or alkoxy each having from 1 to 20 carbon atoms in the
alkyl radical and from 6 to 20 carbon atoms in the aryl radical, or alkoxy with C1-C10-alkyl or C6-C15-aryl,
- rG
- is an integer from 1 to 3
and
- sG and tG
- are integers from 0 to 2, with the sum rG + sG + tG corresponding to the valence of MG ,
where the component E) is not identical to the component C). It is also possible to
use mixtures of various metal compounds of the formula (XX).
[0128] Among the metal compounds of the formula (XX), preference is given to those in which
- MG
- is lithium, magnesium, boron or aluminum and
- R1G
- is C1-C20-alkyl.
[0129] Particularly preferred metal compounds of the formula (XX) are methyllithium, ethyllithium,
n-butyllithium, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium
chloride, ethylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium,
dibutylmagnesium, n-butyl-n-octylmagnesium, n-butyl-n-heptylmagnesium, in particular
n-butyl-n-octylmagnesium, tri-n-hexylaluminum, triisobutylaluminum, tri-n-butylaluminum,
triethylaluminum, dimethylaluminum chloride, dimethylaluminum fluoride, methylaluminum
dichloride, methylaluminum sesquichloride, diethylaluminum chloride and trimethylaluminum
and mixtures thereof. The partial hydrolysis products of aluminum alkyls with alcohols
can also be used.
[0130] When a metal compound E) is used, it is preferably present in the catalyst system
in such an amount that the molar ratio of M
G from formula (XX) to transition metal from monocyclopentadienyl compound A) is from
2 000:1 to 0.1:1, preferably from 800:1 to 0.2:1 and particularly preferably from
100:1 to 1:1.
[0131] In general, the catalyst solid together with the further metal compound E) of the
formula (XX), which may be different from the metal compound or compounds E) used
in the preparation of the catalyst solid, is used as constituent of a catalyst system
for the polymerization or copolymerization of olefins. It is also possible, particularly
when the catalyst solid does not contain any activating component C), for the catalyst
system to further comprise, in addition to the catalyst solid, one or more activating
compounds C) which are identical to or different from any activating compounds C)
present in the catalyst solid.
[0132] To prepare the catalyst systems of the present invention, preference is given to
immobilizing at least one of the components A) and/or C) on the support B) by physisorption
or by means of chemical reaction, i.e. covalent binding of the components, with reactive
groups of the support surface. The order in which the support component B), the component
A) and any component C) are combined is immaterial. The components A) and C) can be
added independently of one another or simultaneously or in premixed form to B). After
the individual process steps, the solid can be washed with suitable inert solvents
such as aliphatic or aromatic hydrocarbons.
[0133] In a preferred embodiment the monocyclopentadienyl complex A) is brought into contact
with the activating compound C) in a suitable solvent, usually giving a soluble reaction
product, an adduct or a mixture. The preparation obtained in this way is then brought
into contact with the support B), which may have been pretreated, and the solvent
is completely or partly removed. This preferably gives a solid in the form of a free-flowing
powder. Examples of the industrial implementation of such a process are described
in
WO 96/00243,
WO 98/40419 or
WO 00/05277. A further preferred embodiment comprises firstly applying the activating compound
C) to the support B) and subsequently bringing this supported activating compound
into contact with the monocyclopentadienyl complex A).
[0134] The component D) can likewise be reacted in any order with the components A) and
optionally B), C) and E). Preference is given to bringing D) firstly into contact
with component C) and then dealing with the components A) and B) and any further C)
as described above. In another preferred embodiment, a catalyst solid is prepared
from the components A), B) and C) as described above and this is brought into contact
with the component E) during, at the beginning of or shortly before the polymerization.
Preference is given to E) firstly being brought into contact with the α-olefin to
be polymerized and the catalyst solid comprising the components A), B) and C) as described
above subsequently being added. The monocyclopentadienyl complex A) can be brought
into contact with the component(s) C) and/or D) either before or after being brought
into contact with the olefins to be polymerized. Preactivation using one or more components
C) prior to mixing with the olefin and further addition of the same or different components
C) and/or D) after the mixture has been brought into contact with the olefin is also
possible. Preactivation is generally carried out at 10-100°C, in particular 20-80°C.
[0135] It is also possible for the catalyst system firstly to be prepolymerized with α-olefins,
preferably linear C
2-C
10-1-alkenes and in particular ethylene or propylene, and the resulting prepolymerized
catalyst solid then to be used in the actual polymerization. The mass ratio of catalyst
solid used in the prepolymerization to monomer to be polymerized onto it is usually
in the range from 1:01 to 1:1 000, preferably from 1:1 to 1:200.
[0136] Furthermore, a small amount of an olefin, preferably an α-olefin, for example vinylcyclohexane,
styrene or phenyldimethylvinylsilane, as modifying component, an antistatic or a suitable
inert compound such as a wax or oil can be added as additive during or after the preparation
of the catalyst system. The molar ratio of additives to transition metal compound
B) is usually from 1:1 000 to 1 000:1, preferably from 1:5 to 20:1.
[0137] The catalyst systems of the present invention are suitable for the polymerization
of olefins and especially for the polymerization of α-olefins, i.e. hydrocarbons having
terminal double bonds. Suitable monomers also include functionalized olefinically
unsaturated compounds such as acrolein, ester or amide derivatives of acrylic or methacrylic
acid, for example acrylates, methacrylates or acrylonitrile, or vinyl esters, for
example vinyl acetate. Preference is given to nonpolar olefinic compounds, including
aryl-substituted α-olefins. Particularly preferred α-olefins are linear or branched
C
2-C
12-1-alkenes, in particular linear C
2-C
10-1-alkenes such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
1-decene or branched C
2-C
10-1-alkenes such as 4-methyl-1-pentene, conjugated and unconjugated dienes such as
1,3-butadiene, 1,5-hexadiene or 1,7-octadiene or vinylaromatic compounds such as styrene
or substituted styrene. It is also possible to polymerize mixtures of various α-olefins.
Preference is given to polymerizing at least one olefin selected from the group consisting
of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene.
[0138] Suitable olefins also include ones in which the double bond is part of a cyclic structure
which can have one or more ring systems. Examples are cyclopentene, cyclohexene, norbornene,
tetracyclododecene and methylnorbornene and dienes such as 5-ethylidene-2-norbornene,
norbornadiene or ethylnorbornadiene.
[0139] Mixtures of two or more olefins can also be polymerized. In contrast to some known
iron and cobalt complexes, the transition metal complexes of the present invention
display a good polymerization activity even in the case of higher α-olefins, so that
their suitability for copolymerization deserves particular emphasis. In particular,
the transition metal complexes of the present invention can be used for the polymerization
or copolymerization of ethene or propene. As comonomers in the polymerization of ethene,
preference is given to using C
3-C
8-α-olefins or norbornene, in particular 1-butene, 1-pentene, 1-hexene and/or 1-octene.
Preference is given to using monomer mixtures containing at least 50 mol% of ethene.
Preferred comonomers in the polymerization of propylene are ethene and/or butene.
[0140] The polymerization can be carried out in a known manner in bulk, in suspension, in
the gas phase or in a supercritical medium in the customary reactors used for the
polymerization of olefins. It can be carried out batchwise or preferably continuously
in one or more stages. High-pressure polymerization processes in tube reactors or
autoclaves, solution processes, suspension processes, stirred gas-phase processes
or gas-phase fluidized-bed processes are all possible.
[0141] The polymerizations are usually carried out at from -60 to 350°C under pressures
of from 0.5 to 4 000 bar at mean residence times of from 0.5 to 5 hours, preferably
from 0.5 to 3 hours. The advantageous pressure and temperature ranges for carrying
out the polymerizations usually depend on the polymerization method. In the case of
high-pressure polymerization processes, which are usually carried out at pressures
of from 1 000 to 4 000 bar, in particular from 2 000 to 3 500 bar, high polymerization
temperatures are generally also set. Advantageous temperature ranges for these high-pressure
polymerization processes are from 200 to 320°C, in particular from 220 to 290°C. In
the case of low-pressure polymerization processes, a temperature which is at least
a few degrees below the softening temperature of the polymer is generally set. These
polymerization processes are preferably carried out at from 50 to 180°C, preferably
from 70 to 120°C. In the case of suspension polymerization, the polymerization is
usually carried out in a suspension medium, preferably an inert hydrocarbon such as
isobutane or a mixture of hydrocarbons, or else in the monomers themselves. The polymerization
temperatures are generally in the range from -20 to 115°C, and the pressure is generally
in the range from 1 to 100 bar. The solids content of the suspension is generally
in the range from 10 to 80%. The polymerization can be carried out batchwise, e.g.
in stirring autoclaves, or continuously, e.g. in tube reactors, preferably in loop
reactors. Particular preference is given to employing the Phillips PF process as described
in
US-A 3 242 150 and
US-A 3 248 179. The gas-phase polymerization is generally carried out at from 30 to 125°C.
[0142] Among the abovementioned polymerization processes, particular preference is given
to gas-phase polymerization, in particular in gas-phase fluidized-bed reactors, solution
polymerization and suspension polymerization, in particular in loop reactors and stirred
tank reactors. The gas-phase polymerization can also be carried out in the condensed
or supercondensed phase, in which part of the circulating gas is cooled to below the
dew point and is recirculated as a two-phase mixture to the reactor. It is also possible
to use a multizone reactor in which two polymerization zones are linked to one another
and the polymer is passed alternately through these two zones a number of times. The
two zones can also have different polymerization conditions. Such a reactor is described,
for example, in
WO 97/04015. The different or identical polymerization processes can also, if desired, be connected
in series so as to form a polymerization cascade, for example as in the Hostalen process.
A parallel reactor arrangement using two or more identical or different processes
is also possible. Furthermore, molar mass regulators, for example hydrogen, or customary
additives such as antistatics can also be used in the polymerizations.
[0143] The monocyclopentadienyl complexes of the present invention and the catalyst systems
in which they are present can also be prepared by means of combinations of methods
or their polymerization activity can be tested with the aid of these combined methods.
[0144] The process of the present invention allows polymers of olefins to be prepared. The
term "polymerization" as used here in the description of the present invention encompasses
both polymerization and oligomerization, i.e. oligomers and polymers having molar
masses Mw in the range from 56 to 10 000 000 can be produced by this process.
[0145] Owing to their good mechanical properties, the olefin polymers prepared using the
catalyst system of the present invention are particularly useful for the production
of films, fibers and moldings.
[0146] The catalysts systems of the present invention have particularly high activities.
Examples
[0147] All syntheses and polymerizations were carried out under a protective nitrogen atmosphere.
[0148] The density [g/cm
3] was determined in accordance with ISO 1183.
[0149] The Staudinger index (η)[dl/g] was determined using an automatic Ubbelohde viscometer
(Lauda PVS 1) in decalin as solvent at 130°C (IS01628 at 130°C, 0.001 g/ml of decalin).
[0150] The NMR spectra were measured on a Bruker DRX 200 (
1H: 200.13 MHz). In
1H-NMR spectra, the signal of the incompletely deuterated part of the solvent used
served as internal standard. All signals were calibrated to the appropriate literature
values.
[0151] Mass spectra were recorded on a Finnigan MAT 8230, and high-resolution mass spectra
were measured on a Micromass CTD ZAB-2F VH spectrometer.
[0152] Abbreviations in the tables below:
- cat.
- catalyst
- t(poly)
- polymerization time
- polymer
- amount of polymer formed
- density
- polymer density
- prod.
- productivity of the catalyst system in g of polymer obtained per mmol of catalyst
(chromium complex) used per hour
- hexene
- whether or not hexene is present during the polymerization
Example 1
1.1. Preparation of 1-benzyl-1H-indene
[0153] A solution of 45.5 ml (0.39 mol) of indene in 400 ml of diethyl ether was cooled
to -20°C and 160 ml of n-butyllithium (2.5 M in hexane, 0.4 mol) were subsequently
added while stirring. The mixture was allowed to warm to room temperature and was
stirred for another four hours at this temperature. The reaction mixture was then
cooled back down to -20°C and a solution of 45 g (0.39 mol) of (chloromethyl)benzene
in 100 ml of diethyl ether was subsequently added. The mixture was allowed to warm
to room temperature and was stirred for another 12 hours at this temperature. The
reaction mixture was hydrolyzed with water, the aqueous phase was separated off from
the organic phase and the aqueous phase was extracted twice with diethyl ether. The
organic phases were combined, dried over magnesium sulfate, filtered and the solvent
was distilled off. The residue obtained in this way was distilled at 120-130°C and
1 torr to give 63.5 g (79%) of 1-benzyl-1
H-indene.
NMR
1H (CDCl
3): 7.49-7.26 (9H); 6.92 (dd, 1 H); 6.56 (dd, 1 H); 3.85 (m, 1 H); 3.23 (dd, 1 H);
2.83 (dd, 1H).
1.2. Preparation of 3-benzyl-1-(1-methylethylidene)-1 H-indene
[0154] A solution of 15.3 ml (75 mmol) of 1-benzyl-1H-indene in 150 ml of tetrahydrofuran
was added while stirring to a suspension of 8 g (0.142 mol) of KOH powder in 150 ml
of tetrahydrofuran which had been cooled to 0°C. The mixture was allowed to warm to
room temperature while stirring and was stirred for a further 30 minutes. 8 ml (0.1
mol) of acetone were then added and the mixture obtained in this way was refluxed
for one hour. The mixture was allowed to cool to room temperature while stirring and
was stirred for a further 12 hours. The reaction mixture was then admixed with 10%
strength phosphoric acid, the aqueous phase was separated off from the organic phase
and the aqueous phase was extracted twice with methylene chloride. The organic phases
was combined, dried over magnesium sulfate, filtered and the solvent was distilled
off. The residue obtained in this way was recrystallized from hexane and gave 10.5
g (57%) of 3-benzyt-1-(1-methylethylidene)-1H-indene.
NMR
1H (CDCl
3): 7.40 -7.27 (9H); 6.59 (s, 1 H); 4.04 (s, 2H), 2.48 (s, 3H); 2.29 (s, 3H).
1.3. Preparation of 2-[2-(1-benzyl-1H-inden-3-yl)-2-methylpropyl]pyridine and 2-[2-(3-benzyl-1H-inden-1-yl)-2-methylpropyl]pyridine
[0155] A solution of 9.8 ml (0.1 mol) of 2-picoline in 50 ml of tetrahydrofuran was cooled
to -20°C and 62.5 ml of n-butyllithium (15% M in hexane, 0.1 mol) were subsequently
added while stirring. The mixture was allowed to warm to room temperature over a period
of 1 hour while stirring. A solution of 24.6 g (0.1 mol) of [2,3]-benzo-4-benzyl-6,6-dimethylfulvene
(3-benzyl-1-(1-methylethylidene)-1
H-indene) in 100 ml of tetrahydrofuran was added to the reaction mixture obtained,
with the temperature being maintained at 20°C. The mixture was stirred at room temperature
for a further 12 hours. The reaction mixture was hydrolyzed with 100 ml of water,
the aqueous phase was seprated off from the organic phase and the aqueous phase was
extracted three times with methylene chloride. The organic phases were combined, dried
over magnesium sulfate, filtered and the solvent was distilled off. The residue obtained
in this way was taken up in 150 ml of benzene, filtered and the solvent was distilled
off again to leave 26.1 g (77%) of a mixture of 2-[2-(1-benzyl-1
H-inden-3-yl)-2-methylpropyl]pyridine and 2-[2-(3-benzyl-1
H-inden-1-yl)-2-methylpropyl]pyridine.
NMR
1H (CDCl
3): 8.55 (m, 1H); 7.80-5.95 (13H); 3.95-2.25 (5H); 1.42 (s, 3H); 1.37 (s, 3H) and 8.58
(m, 1H); 7.80-6.36 (13H); 3.95-2.25 (5H); 1.13 (s, 3H); 1.07 (s, 3H).
1.4. Preparation of 3-benzyl-1-(1,1-dimethyl-2-(2-pyridyl)ethyl)indenylchromium dichloride
[0156]
[0157] A solution of 21.4 g (62 mmol) of the isomer mixture from example 1.3. in 370 ml
of diethyl ether and 40 ml of tetrahydrofuran was cooled to -100°C and 40 ml of n-butyllithium
(15% in hexane, 64 mmol) were subsequently added while stirring. After the addition
was complete, the reaction mixture was stirred at this temperature for a further one
hour and then warmed to room temperature and stirred at room temperature for 4 hours.
The reaction mixture was then cooled to -60°C, 23.8 g (64 mmol) of chromium trichloride
tris(tetrahydrofuran) were subsequently added while stirring and the mixture was slowly
warmed to room temperature again. It was stirred for a further 12 hours at room temperature,
refluxed for one hour and then cooled back down to room temperature. The precipitated
formed was filtered off, washed twice with ether, dried and subsequently extracted
with hot methylene chloride. The solvent was distilled off and the residue was dried
under reduced pressure. This gave 16.1 g of 3-benzyl-1-(1,1-dimethyl-2-(2-pyridyl)ethyl)indenylchromium
dichloride (56%).
Example 2
2.1. Preparation of 1-(2-fluorobenzyl)-1H-indene
[0158] A solution of 40.64 ml (0.35 mol) of indene in 400 ml of diethyl ether was cooled
to -30°C and 187.5 ml of n-butyllithium (15% in hexane, 0.3 mol) were subsequently
added while stirring. This mixture was allowed to warm to room temperature and was
stirred for another five hours at this temperature. The reaction mixture was then
cooled to -60°C and a solution of 35.6 g (0.3 mol) of 1-(chloromethyl)-2-fluorobenzene
in 100 ml of diethyl ether was subsequently added. The mixture was allowed to warm
to room temperature and was stirred for another 12 hours at this temperature. The
reaction mixture was hydrolyzed with water, the aqueous phase was separated off from
the organic phase and the aqueous phase was extracted twice with diethyl ether. The
organic phases were combined, dried over magnesium sulfate, filtered and the solvent
was distilled off. The residue obtained in this way was distilled at 120-122°C and
0.5 torr to give 54.8 g (82%) of 1-(2-fluorobenzyl)-1
H-indene.
NMR
1H (CDCl
3): 7.44-7.10 (8H); 6.87 (d, 1H); 6.50 (d, 1H); 3.85 (t, 1H); 3.27 (dd, 1H); 2.80 (dd,
1H).
2.2. Preparation of 2-{[3-(2-fluorobenzyl)-1H-inden-1-yl]methyl}pyridine and 2-{[1-(2-fluorobenzyl)-1H-inden-3-yl]methyl}pyridine
[0159] A solution of 31.36 g (0.14 mol) of 1-(2-fluorobenzyl)-1
H-indene in 420 ml in diethyl ether was cooled to -40°C and 87.7 ml of n-butyllithium
(15% in hexane, 0.14 mol) were subsequently added while stirring. The mixture was
allowed to warm to room temperature and was stirred for another four hours at this
temperature. The reaction mixture was then cooled to -50°C and a solution of 17.84
g (0.14 mol) of 2-(chloromethyl)pyridine in 100 ml of benzene was subsequently added.
The mixture was allowed to warm to room temperature and was stirred for another 12
hours at this temperature. The reaction mixture was hydrolyzed with 200 ml of water,
the aqueous phase was separated off from the organic phase and the aqueous phase was
extracted three times with methylene chloride. The organic phases were combined, dried
over magnesium sulfate, filtered and the solvent was distilled off. The residue obtained
in this way was taken up in 150 ml of benzene, filtered and the solvent was distilled
off again to leave 32.6 g (74%) of a mixture of 2-{[3-(2-fluorobenzyl)-1
H-inden-1-yl]methyl}pyridine and 2-{[1-(2-fluorobenzyl)-1
H-inden-3-yl]methyl}pyridine.
NMR
1H (CDCl
3): 8.75 (m, 1H); 7.65 (dt, 1H); 7.50-7.12 (10H); 6.30 (br.s, 1H); 4.21 (m, 1H); 4.05
(br.s, 2H); 3.40 (dd, 1H); 3.08 (dd, 1H) and 8.70 (m, 1H); 7.60 (dt, 1H); 7.50-7.12
(10H); 6.36 (br.s, 1 H); 4.24 (br.s, 2H); 3.96 (m, 1 H); 3.38 (dd, 1 H); 2.97 (dd,
1 H).
2.3. Preparation of 1-(2-fluorophenylmethyl)-3-(2-pyridylmethyl)indenylchromium dichloride
[0160]
[0161] A solution of 32 g (0.1 mol) of the isomer mixture from Example 2.2. in 320 ml of
tetrahydrofuran was cooled to -100°C and 64 ml of n-butyllithium (15% in hexane, 0.1
mol) were subsequently added while stirring. After the addition was complete, the
reaction mixture was stirred for a further one hour at this temperature and was then
warmed to room temperature and stirred at room temperature for 2 hours. The reaction
mixture was then cooled to -60°C, 38 g (0.1 mol) of chromium trichloride tris(tetrahydrofuran)
were subsequently added while stirring and the mixture was slowly warmed to room temperature
again. It was stirred for a further 12 hours at room temperature, refluxed for 1.5
hours and then cooled back down to room temperature. The precipitate formed was filtered
off, washed twice with ether, dried and subsequently extracted with hot methylene
chloride. The solvent was distilled off and the residue was dried under reduced pressure.
This gave 19.8 g of 1-(2-fluorophenylmethyl)-3-(2-pyridylmethyl)indenylchromium dichloride
(45%).
Example 3
3.1. Preparation of 1-[2-(trifluoromethyl)benzyl]-1H-indene
[0162] A solution of 4.5 ml (39 mmol) of indene in 50 ml of diethyl ether was cooled to
-30°C and 21.7 ml of n-butyllithium (15% in hexane, 35 mmol) were subsequently added
while stirring. The mixture was allowed to warm to room temperature and was stirred
for another five hours at this temperature. The reaction mixture was then cooled to
-60°C and 5 g (26 mmol) of 1-(chloromethyl)-2-(trifluoromethyl)benzene were subsequently
added. The mixture was allowed to warm to room temperature and was stirred for another
12 hours at this temperature. The reaction mixture was hydrolyzed with water, the
aqueous phase was separated off from the organic phase and the aqueous phase was extracted
twice with diethyl ether. The organic phases were combined, dried over magnesium sulfate,
filtered and the solvent was distilled off. The residue obtained in this way was distilled
at 123-125°C and 0.5 torr to give 6.05 g (85%) of 1-[2-(trifluoromethyl)benzyl]-1
H-indene.
NMR
1H (CDCl
3): 7.76 (d, 1H); 7.57-7.23 (7H); 6.88 (dd, 1H); 6.46 (dd, 1H); 3.80 (m, 1H); 3.52
(dd, 1H); 2.76 (dd, 1H).
3.2. Preparation of 2-({3-[2-(trifluoromethyl)benzyl]-1H-inden-1-yl}methyl)pyridine
and 2-({1-[2-(trifluoromethyl)benzyl]-1H-inden-3-yl}methyl)pyridine
[0163] A solution of 6.05 g (22 mmol) of 1-[2-(trifluoromethyl)benzyl]-1
H-indene in 70 ml of diethyl ether was cooled to -40°C and 13.8 ml n-butyllithium (15%
in hexane, 22 mmol) were subsequently added while stirring. The mixture was allowed
to warm to room temperature and was stirred for another four hours at this temperature.
The reaction mixture was then cooled to -50°C and a solution of 2.81 g (22 mmol) of
2-(chloromethyl)pyridine in 15 ml benzene was subsequently added. The mixture was
allowed to warm to room temperature and was stirred for another 12 hours at this temperature.
The reaction mixture was hydrolyzed with 50 ml of water, the aqueous phase was separated
off from the organic phase and the aqueous phase was extracted three times with methylene
chloride. The organic phases were combined, dried over magnesium sulfate, filtered
and the solvent was distilled off. The residue obtained in this way was taken up in
40 ml of benzene, filtered and the solvent was distilled off again to give 7.67 g
(95%) of a mixture of 2-({3-[2-(trifluoromethyl)benzyl]-1
H-inden-1-yl}methyl)pyridine and 2-({1-[2-(trifluoromethyl)benzyl]-1
H-inden-3-yl}methyl)pyridine.
NMR
1H (CDCl
3): 8.65 (m, 1H); 7.60 (dt, 1H); 7.40-7.01 (10); 6.15 (br.s, 1H); 4.01 (m, 1H); 3.93
(br.s, 2H); 3.28 (dd, 1H); 2.96 (dd, 1H) und 8.60 (m, 1H); 7.54 (dt, 1H); 7.50-7.12
(10H); 6.23 (br.s, 1H); 4.11 (br.s, 2H); 3.84 (m, 1H); 3.25 (dd, 1H); 2.84 (dd, 1
H).
3.3. Preparation of 3-(2-(trifluoromethyl)phenylmethyl)-1-(1-(2-pyridyl)methyl)indenylchromium
dichloride
[0164]
[0165] A solution of 7.67 g (21 mmol) of the isomer mixture from Example 3.2. in 60 ml of
tetrahydrofuran was cooled to -100°C and 13.1 ml of n-butyllithium (15% in hexane,
21 mmol) were subsequently added while stirring. After the addition was complete,
the reaction mixture was stirred at this temperature for a further one hour and then
warmed to room temperature and stirred at room temperature for 2 hours. The reaction
mixture was then cooled to -60°C, 7.86 g (21 mol) of chromium trichloride tris(tetrahydrofuran)
were subsequently added while stirring and the mixture was slowly warmed to room temperature
again. It was stirred for a further 12 hours at room temperature, refluxed for 1 hour
and then cooled back down to room temperature. The precipitate formed was filtered
off, washed twice with ether, dried and subsequently extracted with hot methylene
chloride. The solvent was distilled off and the residue was dried under reduced pressure.
This gave 1.9 g of 3-(2-(trifluoromethyl)phenylmethyl)-1-(1-(2-pyridyl)methyl)indenyl-chromium
dichloride (19%).
Example 4
4.1. Preparation of 1-(1 H-inden-1-ylmethyl)naphthalene
[0166] A solution of 17.4 g (0.15 mol) of indene in 200 ml of diethyl ether was cooled to
-30°C and 94 ml of n-butyllithium (15% in hexane, 0.15 mol) were subsequently added
while stirring. The mixture was allowed to warm to room temperature and was stirred
at this temperature for another five hours. The reaction mixture was then cooled to
0°C and a solution of 26.5 g (0.15 mol) of 1-(chloromethyl)naphthalene in 50 ml of
diethyl ether was subsequently added. The mixture was allowed to warm to room temperature
and was stirred for another 12 hours at this temperature. The reaction mixture was
hydrolyzed with water, the aqueous phase was separated off from the organic phase
and the aqueous phase was extracted twice with diethyl ether. The organic phases were
combined, dried over magnesium sulfate, filtered and the solvent was distilled off.
This gave 36.6 g (95%) of 1-(1H-inden-1-ylmethyl)naphthalene.
NMR
1H (CDCl
3): 8.28 (d, 1 H); 8.00 (d, 1 H); 7.88 (d, 1 H); 7.66-7.26 (group of signals, 8H);
6.90 (dd, 1H); 6.49(dd, 1H); 4.00 (m, 1H); 3.71 (dd, 1H); 3.13 (dd, 1H).
4.2. Preparation of 2-{[3-(1-naphthylmethyl)-1H-inden-1-yl]methyl}pyridine and 2-{[1-(1-naphthylmethyl)-1H-inden-3-yl]methyl}pyridine
[0167] A solution of 30.7 g (0.12 mol) of 1-(1H-inden-1-ylmethyl)naphthalene in 250 ml diethyl
ether was cooled to 0°C and 82 ml of n-butyllithium (15% in hexane, 0.13 mol) were
subsequently added while stirring. The mixture was allowed to warm to room temperature
and was stirred for another two hours at this temperature. The reaction mixture was
then cooled to -40°C and a solution of 15.3 g (0.12 mol) of 2-(chloromethyl)pyridine
in 45 ml of benzene was subsequently added. The mixture was allowed to warm to room
temperature and was stirred for another 12 hours at this temperature. The reaction
mixture was hydrolyzed with 100 ml of water, the aqueous phase was separated off from
the organic phase and the aqueous phase was extracted three times with methylene chloride.
The organic phases were combined, dried over magnesium sulfate, filtered and the solvent
was distilled off. The residue obtained in this way was taken up in 150 ml of benzene,
filtered and the solvent was distilled off again to give 40 g (96%) of a mixture of
2-{[3-(1-naphthylmethyl)-1H-inden-1-yl]methyl}pyridine and 2-{[1-(1-naphthytmethyt)-1H-inden-3-yl]methyl}pyridine.
NMR
1H (CDCl
3): 8.70 (m, 1H); 8.18-7.04 (14H); 6.08 (m, 1H); 4.43 (br.s, 2H); 4.17 (m, 1H); 3.36
(dd, 1H); 3.02 (dd, 1H) and 8.72 (m, 1H); 8.34-7.17 (14H); 6.29 (m, 1H); 4.23 (br.s,
2H); 4.09 (m, 1H); 3.77 (dd, 1 H); 3.27 (dd, 1H).
4.3. Preparation of 3-((1-naphthyl)methyl)-1-((2-pyridyl)methyl)indenylchromium dichloride
[0168]
[0169] A solution of 35 g (0.1 mol) of the isomer mixture from Example 4.2. in 300 ml of
tetrahydrofuran was cooled to -20°C and 64 ml of n-butyllithium (15% in hexane, 0.1
mol) were subsequently added while stirring. After the addition was complete, the
reaction mixture was warmed to room temperature and stirred for 3 hours. The reaction
mixture was then cooled to -60°C, 38 g (0.1 mol) of chromium trichloride tris(tetrahydrofuran)
were subsequently added while stirring and the mixture was slowly warmed to room temperature
again. It was stirred for a further 12 hours at room temperature, refluxed for 30
minutes and then cooled back down to room temperature. The precipitate formed was
filtered off, washed twice with ether, dried and subsequently extracted with hot methylene
chloride. The solvent was distilled off and the residue was dried under reduced pressure.
This gave 8.3 g of 3-((1-naphthyl)methyl)-1-((2-pyridyl)methyl)indenylchromium dichloride
(18%).
Comparative Example 1
[0170] 1-(2-Pyridylmethyl)indenylchromium dichloride was prepared as described in
WO 2004/056482.
Comparative Example
[0171] 1-(2-Pyridylmethyl)-3-tert-butylindenylchromium dichloride was prepared by a method
analogous to that described in
WO 2004/056482 using 1-tert-butylindene.
Examples 5-8
Polymerization
[0172] The polymerizations were carried out at 40°C under argon in a 1 I four-neck flask
provided with contact thermometer, stirrer with Teflon blade, heating mantle and gas
inlet tube. The appropriate amount of MAO (30% strength solution in toluene, Cr:Al
as in Table 1) was added to a solution of the amount indicated in Table 1 of the appropriate
complex in 250 ml of toluene and the mixture was heated to 40°C on a water bath.
[0173] In the ethylene homopolymerizations, ethylene was passed through the solution at
a flow rate of from 20 to 20 l/h at atmospheric pressure. After maintaining a constant
ethylene flow for the time indicated in Table 1, the polymerization was stopped by
addition of methanolic HCl solution (15 ml of concentrated hydrochloric acid in 50
ml of methanol). 250 ml of methanol were subsequently added and the white polymer
formed was filtered off, washed with methanol and dried at 70°C.
Table 1: Polymerization results
Ex. |
Cat. from Ex. |
Amount of cat. [mg] ([µmol]) |
Cr:Al |
t(poly) [min] |
Polymer [g] |
Prod. [g/(mmol M.h)] |
5 |
3 |
8.3 (17) |
1:500 |
10 |
6.1 |
2153 |
6 |
4 |
11.8 (25.1) |
1:500 |
7 |
7.7 |
2631 |
7 |
C1 |
7.2 (21.9) |
1:500 |
15 |
3.1 |
556 |
8 |
C2 |
10.2 (26.5) |
1:500 |
10 |
6.6 |
1496 |